Luminescent metal complexes containing naphthalene and anthracene units 4

Chapter Synthesis, Structures and photooxidation of Pt(II)- and Pd(II)-1.8-bis(diphenylphophosphino)anthraceneComplexes 97 4.1 Introduction As mentioned in the previous chapter, the photochemistry, especially the photooxidation of d8 PtII complexes is very rich. Described in this chapter is the synthesis of a reported diphosphine 1,8-bis(diphenylphosphino)anthracene (DAP) and its Pt(II) and Pd(II) complexes. The structures, electronic spectroscopy, luminescence photochemical reactivity of the complexes were examined. Particularly, the photooxidations of the complex Pt(DAP)Cl were studied in details. The results showed a neat photoinduced four-electron reduction of oxygen. Organoplatinum(II) Pt(PCP)Cl (PCP = 1, 3-bis(diphenylphosphino)benzene) is shown in Scheme 4.1, which contains a pincer type ligand. Ph2P Pt PPh2 Cl Scheme 4.1 Pt(PCP)Cl 4.2 Result and Discussion 4.2.1 Synthesis of 1, 8-bis(diphenylphosphino)anthracene 1,8-bis(diphenylphosphino)anthracene (DAP) cannot be synthesized through the usual way from 1,8-dichloroanthracene. It is impossible to convert 1,8-dichloroanthracene by twofold metallation into the dilithium compound by n-Buli or the di-Grignard compound, and then substitute the metal by diphenylphosphine. It can be obtained in moderate yield of 33% by reaction of potassium anthracene disulfonate with two equivalents potassium diphenylphosphide (Ph2PK) in diethylene glycol diethyl under harsh reaction conditions (180°C, 20h).1 A relatively simple method was developed by Haenel.2 1,8-difluroanthracene was prepared from the commercially available 1,8-dichloro-9,10-anthraquinone in a two-step synthesis. 1,8- 98 difluroanthracene as starting materials is proved to be highly reactive for nucleophilic displacement of the fluoro substituents by alkali metal phosphides. Reaction with two equivalents potassium diphenylphosphine, 1,8-difluroanthracene was converted to 1,8- bis(diphenylphosphino)anthracene with high yield (51%, three steps). It is a yellow powder with strong smell, which can dissolve well in aprotic solutions such as CH2Cl2 or CHCl3. The 1H NMR and 31P NMR (CDCl3, 121.4M Hz) are consistent with the reported result. 1,2 In the 1H- NMR spectrum (CDCl3, 300M Hz) of PCP ligand the signals of the anthracene 9,10-H are widely separated (δ = 9.80 ppm and 8.45 ppm). Other protons of anthracene locate at 7.97 ppm, 7.78 ppm and 7.29 ppm. The phenyl protons are in the range of 7.32-7.40 ppm. In 31 P{1H}-NMR spectrum (CDCl3, 121.5M Hz) shows a singlet at -14.6 ppm. Another way to synthesized the DAP ligand is to get 1-fluro-8-phenylphosphinoantracene by reaction of 1,8-difluroanthracene and sodium diphenylphosphine at first, then convert 1-fluro-8-phenylphosphinoantracene to DAP using excess sodium diphenylphosphine in dioxane. Yield is 35%. 4.2.2 Synthesis and Structure of Pt(DAP)Cl (4.1) The complex can be prepared by refluxing either a chloroform solution of DAP with mol equiv of PtCl2(CH3CN)2 or a CH3CN/H2O mixture of DAP and K2PtCl4 for day. Addition of excess diethyl ether to the solution precipitated the product Pt(DAP)Cl as pale yellow powders. The complex can dissolve well in aprotic solutions such as CH2Cl2, CHCl3 and DMF but it is only sparingly soluble in CH3OH and CH3CN. Orange crystals were obtained by slow evaporation of acetonitrile solution of the complex. The structure was confirmed by single crystal X-ray diffraction. 99 Figure 4.1 ORTEP plot of 4.1·CH3CN. Thermal ellipsoids are drawn with 50% probability. The hydrogen atoms and solvent are omitted for clairity. The X-ray crystal structure of Pt(DAP)Cl and the selected bond lengths and angles are shown in Figure 4.1 and Table 4.1, respectively. The complex displays an approximate C2v symmetry in which the platinum atom adopts a distorted square-planar coordination geometry which is typical for Pt(II) compounds. The metal atom is coordinated to the two P atoms of DAP and the deprotonated C(9) of anthracenyl ring. A chloride ion coordinates trans to the carbon atom. The C(9)-Pt-Cl(1) linkage is nearly linear (177.54(10)°). However, The P(1)-Pt-P(2) angle of deviates significantly from linearity. The angle of P(2)-Pt(1)-C(9) of 83.70°, P(1)-Pt(1)-C(9) of 83.79°, P(2)-Pt(1)-Cl(1) of 94.53° and P(2)-Pt(1)-Cl(1) of 97.92° deviate from 90°. Compared with the angle of N-Pt-N (78.1(4)°) and N-Pt-P (105.4(3)°) in other Pt(II) complexes like [Pt(CNN)PPh3]+ (CNN=6-phenyl-2,2’-bypridine),3 The square plane is not distorted greatly. The data are very close to the structure of Pt(PCP)Cl (PCP = 1, 3-bis(diphenylphosphino)benzene), 4b (C-Pt-P = 82.3(3)° and P-Pt-Cl = 99.44(9)°). The torsion angle of P(2)-C(3)-C(9)-Pt(1) is 1.15° and P(1)-C(1)-C(9)-Pt(1) is 0.05° show three bonds, Pt(1)-C(9), C(8)-P(2) and C(1)-P(1) are almost parallel. The Pt-C(9) distance of 1.991(3) Å is similar to the bond distances observed in other cyclometallated Pt(II) complexes such as Pt(PCP)(CF2CF2CF3) (PCP = 1, 3- 100 bis(diphenylphosphino)benzene).4a The distance from Pt to the arene is 2.072(7) Å. In Pt(PCP)X ( X=Cl, Br, CO2H), the Pt-C is in the range of 2.003(9)-2.066(3) Å.4b The bond average Pt-P distance is 2.2685 Å. Compared with other Pt complexes, Pt-P is in the range of 2.275-2.381 Å, such as 2.2753(12)-2.3159(10) Å in Pt(PCP)+ ( PCP= [C6H3(CH2PPh2)2-2,6]-),5 these bond lengths are in the normal range.6 Pt(1)-Cl(1)= 2.3914(9) is also in the same range. The average Pt-Cl distance is 2.324(2) Å, 2.309(3) Å and 2.317(1) Å in cis-[PtCl2(1,4-thioxane)2], cis[PtCl2(DMSO)2] and cis-[PtCl2(dms)2] sequently.7 Pt-Cl bond is 2.384(2) Å in the PtPh(PPh2)2Cl.4b Side view of 4.1·CH3CN in Figure 4.2 shows the main framework is highly planar. The mean deviation of C atom on anthracenyl ring plane is only 0.0272 Å. It has extremely small dihedral angle of 1.75° between the lateral rings of anthracene. The two P atoms are also coplanar with the anthracenyl rings as they are on the same side of anthracenyl plane. The distance from the anthracenyl ring is 0.0334 Å and 0.0636 Å respectively. The deviation of the Pt atom from anthracene plane is -0.0203 Å which is on the opposite side of two P atoms and Cl atom. The Cl atom has a 0.0757 Å deviation to the anthracene. Figure 4.2 ORTEP diagrams showing the side view of 4.1·CH3CN Thermal ellipsoid are drawn with 50% probability. All the hydrogen atoms and solvent are omitted for clarity. 101 Table 4.1 Selected bond length(Å) and angles(deg) of 4.1 Bond Lengths Pt(1)-C(9) Pt(1)-P(2) Pt(1)-P(1) Pt(1)-Cl(1) P(1)-C(1) P(2)-C(8) C(9)-C(11) C(9)-C(13) C(13)-C(8) C(13)-C(14) C(12)-C(7) C(1)-C(11) 1.991(3) 2.2664(9) 2.2705(9) 2.3914(9) 1.809(4) 1.803(4) 1.411(5) 1.413(5) 1.432(5) 1.435(5) 1.435(5) 1.441(5) Bond angles C(9)-Pt(1)-P(2) C(9)-Pt(1)-P(1) P(2)-Pt(1)-P(1) C(9)-Pt(1)-Cl(1) P(2)-Pt(1)-Cl(1) P(1)-Pt(1)-Cl(1) C(11)-C(9)-C(13) C(11)-C(9)-Pt(1) C(13)-C(9)-Pt(1) C(7)-C(8)-P(2) C(13)-C(8)-P(2) C(2)-C(1)-P(1) 83.79(10) 83.70(10) 167.34(3) 177.54(10) 94.53(3) 97.92(3) 117.3(3) 121.5(2) 121.2(2) 127.0(3) 112.0(2) 127.6(3) Compared with 1H NMR and 31P NMR of DAP ligand, 4.1 has quite different peak shift. In 1H NMR (300 MHz, CDCl3), because forming C-Pt bond, the former 9-H in 1,8bis(diphenylphosphino)anthracene disappeared. In the 1H-NMR spectrum (CDCl3, 300 M Hz) of PCP ligand, the signals of the anthracene 9,10-H are widely separated (δ = 9.80 and 8.45). The assignment of the lower-field signal to 9-H located between the two phosphorus groups is based on the chemical shift differing considerable from the usual range of the anthracene 9,10-H and the abnormally large coupling constant to phosphorus (JP,H = 5.2 Hz). In the most stable conformation enforced by the bulk of the phenyl substitute, the phosphorus long pairs are oriented toward 9-H, thus causing a strong downfield shift and enabling space coupling.1,8 After forming the cyclometallated platinum complexes, the signal for the anthracene 9-H disappeared. A triplet peak appears at 8.35 ppm with J = 2.4 Hz which is assigned as 10-H, which is caused by JPt, H or the P atoms. The 8.35(d, JH,H = 8.1 Hz, 2H, H4,5), 7.79(m, 2H, H2,7), 7.54(dd, JH,H = JH,H = 8.1 Hz, 2H, H3,6) is assigned as the proton on the 4,5-H, 2,7-H, and 3,6-H on the anthracene. The protons of phenyl ring have chemical shift at 7.95(m) and 7.43(m), the integration is consistent with complex. The 31 P{1H}NMR(CDCl3, 121.5 MHz) spectrum shows a singlet at 39.8 ppm. The resonance of coupling signals due to 195 Pt (natural abundance 34%; JPtP = 2994.4 Hz) unambiguously demonstrates coordination of the phosphine donors to the metal. The FABMS show the existence of molecular peak at 776.1(93%) and Pt(DAP)+ peak at 740.1(100%). 102 a) b) Figure 4.3 ORTEP diagrams of 4.1· CH3CN showing (a) the top view and (b) the side view of the 4.1·CH3CN in a dimer Two face-to-face overlapped aromatic rings have typical π-π interaction once the interplanar distance of these two planes is 3.3-3.8 Å. The edge-to-face C•••H― π interaction exists when the centroids of the lateral ring separate the ring containing the interacting H atoms 103 below Å. The angle of two aromatic rings is close to 90°. The distance between the proton and the centroid of the lateral is nearly Å9. In the 4.1·CH3CN crystal lattice shown in Figure 4.3, there are pairs of complexes stacked in a head-to-tail fashion. The two Pt(DAP)Cl units are nearly parallel to each other as suggested by the dihedral angle of 0.4° of two anthracenyl planes. The distance of two parallel anthracene in the dimer is 3.459 Å and the distance of centroids of these two anthracenyl ring is 3.656 Å, which is strongly supported the face-to-face π-π interaction. Except for the neighboring anthracene plane, an edge-to-face interaction also exists between the C-H of anthracene and the closest phenyl ring. The distance from the centroid of lateral ring to the phenyl ring is 5.385 Å and 4.877 Å. The H4, to the centroids of phenyl ring is 3.366 Å and 2.611 Å, respectively. Anthracenyl plane and phenyl ring have the dihedral angle of 66.6° and 69.9°, separately. The former edge-to–face interaction can be ignored. As demonstrated by the comprehensive surveys of Dance and Scudder, edge-to-face Ph-Ph interactions, also known as “phenyl embrace”, widely occur in the crystals of metal complexes containing PPh3 or diphosphines.9e,10,11 There is no close Pt-Pt interaction between adjacent complexes. The Pt-Pt distance of two molecular with π- π interaction is 8.326 Å. Figure 4.3 clearly shows the existence of π-π interaction between the two frameworks. Figure 4.4 shows the molecules pack as head-to-tail in a dimer, each molecule of the dimer related to the other by a center of inversion. The dimmer has a plane-to-plane separation of 3.459 Å. 104 Figure 4.4 Crystals packing of 4.1·CH3CN. Hydrogen atoms and solvent are omitted for clarity. One dimer is displayed. 4.2.3 Synthesis and Structure of Pt(DAP)X (X= Br or I) The chloride ion in 4.1·CH3CN can be substituted by bromide or iodide by stirring a CH2Cl2/CH3OH (v/v =1:1) solution of complex 4.1·CH3CN and excess KX (X = Br or I) for days at room temperature (equation 4.1) Pt(DAP)Cl + KX (excess) → Pt(DAP)X + KCl equation 4.1 The yields of Pt(DAP)Br (4.2·CH2Cl2) and Pt(DAP)I (4.3·CH2Cl2) are 85% and 70%, respectively. The solubility of the complexes in organic solvents is similar to that of 4.1·CH3CN. Blocks of orange crystals qualified for X-ray diffraction studies were obtained by slow diffusion of hexane into dichloromethane solution of the compounds. As expected, the structures of the two complexes are similar to that of Pt(DAP)Cl (Figures 4.5 and 4.6). Selected bond lengths and angles of the two complexes are listed in Tables 4.2 and 4.3, respectively. 105 Figure 4.5 ORTEP diagrams of 4.2·CH2Cl2. Thermal ellipsoid are drawn with 50% probability. All the hydrogen atoms and solvent inside are omitted Figure 4.6 ORTEP diagrams of 4.3·CH2Cl2. Thermal ellipsoid are drawn with 50% probability. All the hydrogen atoms and solvent inside are omitted 106 Figure 4.63 ORTEP diagram of 4.9, top view. Themal ellipsoids are drawn with 50% probability. All the hydrogen atoms are omitted Figure 4.64 ORTEP diagram of 4.9 along P-Pt-P axis. Themal ellipsoids are drawn with 50% probability. All the hydrogen atoms are omitted 184 The bond of Pt-P are 2.3423(7) Å and 2.3517(7) Å, and the Pt(1)-C(9) distance is 2.021(3) Å, which is longer than the bond length Pt-C of 4.1. Compared with other Pt(IV) complexes, the Pt(IV)-C is close to the other Pt(IV) complexes, e.g. in PtClMe2(CHNMe2)(tbu2bpy)]Cl, (2.129((15) Å)47 and [PtBrMe2(CH2R)(bu2bipy)] (2.071-2.090 Å)48. The mean bond length of Pt(I)-Cl is 2.33 Å, close to [PtCl4(NCNR2)2] ( 2.297-2.321 Å)(R=Me, Et, C5H10, OC4H8)49. The nearest Pt(IV)-Pt(IV) is 9.937 Å. Some of bond length and angles are listed in Table 4.14. In ESI-MS, molecular peak can be observed at 882(M+, 35%), use 20% energy to attack this peak, 773(M-3Cl-, 65%) can be observed. In FAB-MS, a peak at 882.0 also shows the existence of molecule, and lose one to three Cl- at 845 (64%), 810(88%), 785(60%). Table 4.14 Selected bond length(Å) and angles(deg) for the compound 4.9 Pt(1)-C(9) Pt(1)-Cl(4) Pt(1)-Cl(3) Pt(1)-P(2) Pt(1)-P(1) Pt(1)-Cl(2) P(1)-C(1) P(2)-C(8) C(9)-C(11) C(9)-C(13) C(1)-C(11) Bond Lengths 2.021(3) 2.3274(8) 2.3309(7) 2.3423(7) 2.3517(7) 2.4254(7) 1.806(3) 1.809(3) 1.399(4) 1.401(4) 1.426(4) C(9)-Pt(1)-Cl(4) C(9)-Pt(1)-Cl(3) Cl(4)-Pt(1)-Cl(3) C(9)-Pt(1)-P(2) Cl(4)-Pt(1)-P(2) Cl(3)-Pt(1)-P(2) C(9)-Pt(1)-P(1) Cl(4)-Pt(1)-P(1) Cl(3)-Pt(1)-P(1) P(2)-Pt(1)-P(1) C(9)-Pt(1)-Cl(2) Cl(4)-Pt(1)-Cl(2) Bond angles 88.55(8) 86.73(8) 175.23(3) 84.23(7) 92.21(3) 86.60(3) 83.89(7) 87.63(3) 92.59(3) 168.12(2) 178.54(8) 92.71(3) In CHCl3, the Pt(II) can be oxidized in Pt(IV) by oxidative addition50, 51. The reaction between the Pt complex and CHCl3 first involves electron transfer from Pt(II) to CHCl3 to form CHCl2 (radical) and Cl ion. The Cl ion combines with the Pt(III) to form the intermediate Pt(III)Cl complex which transfers another electron to chloroform to form CHCl2 radical and chloride ion and the recombination of the chloride and the Pt(IV) gives the product. The CHCl2 radical could be responsible for the abstraction of a H atom at C10 position. The carbon radical formed would abstract a chlorine atom from the solvent (Figure 4.65). 185 CHCl3 CHCl3 Ph2P PtII Ph2P PPh2 CHCl2 Cl III Pt Ph2P PPh2 Cl Cl CHCl2 Cl PtIV PPh2 Cl Cl CHCl2 Cl ClPh2P Cl Figure 4.65 PtIV Cl PPh2 Ph2P Cl Cl PtIV PPh2 Cl Cl Proposed mechanism of formation 4.9 Complex 4.9 is orange solid which is also show strong absorption and luminescent in solvent. Its UV-vis absorption (Figure 4.66) shows that it has similar absorption as complex 4.1. However, the peaks have a blue shift and absorption is weaker than 4.1. Complexes 4.9 has high energy at λ< 300 nm (εmax > 105 M-1cm-1). It is assigned to π→π* of 9-chloro-1,8bis(diphenyulphosphino)anthracene. There are moderately intense bands which is also attributable to π→π* transition of the anthracenyl ring between 330-450nm. Table 4.15 the UV-Absorption data of 4.1 and 4.9 λabs [nm] (ε= mol-1dm3cm-1)a complex 4.1 4.9 a 238(52256), 279(64330), 379(2108), 429(6453), 454(7147), 516(38), 643(18), 703(27) 273.5(33758),336(2819),395.5(1765),417.5(2631),443(2419) in CH2Cl2 at 298 K 186 3.5x10 -1 2.5x10 Extinction Coefficient(M .cm ) -1 3.0x10 2.0x10 1.5x10 1.0x10 5.0x10 0.0 250 300 350 400 450 500 550 Wavelength(nm) Figure 4.66 UV-vis absorption spectrum of 4.9 in CH2Cl2(C=5.72x10-5 mol/l) at room temperature The complex 4.9 shows emissions maximize at 497 nm (Figure 4.67). The emissions show poorly resolved vibronic spacing of ~1154 cm-1 which could be attributable to the averaged frequency of the C=C stretches of anthracenyl ring in the excited state. 28 The strong emission is assigned to the 3ππ* intraligand excited state localized in the anthracenyl ring. 300 Emission Intensity(A.U.) 250 200 150 100 50 450 500 550 600 650 700 Wavelength(nm) Figure 4.67 The emission of 4.9 at 298 K. Solvent: CH2Cl2 (degassed). T: 298 K. Excitation wavelength=430 nm, Excitation and Emission slit widths: nm. 187 4.4 Experimental Section General Method. All of the syntheses were carried out in N2 atmosphere with standard Schlenck techniques. PtCl2(CH3CN) and PdCl2(CH3CN) were synthesized according to the reported methods.52,53 1, 8-dichloroanthraquione and CDCl3 were purchased from Aldrich and used without being purified. K2PtCl4 was purchased from Oxkem. The solvent THF, CH2Cl2, CHCl3, dioxane is from Tedica company. PPh3, PPh2Cl, CeF2, HC≡CPh, AgCF3SO3 are from Acros Organics Company. Physical measurements: The UV/Vis absorption and emission spectra of the complexes were recorded on a Hewlett-Packard HP8452A diode array spectrophotometer and a Perkin-Elmer LS50D fluorescence spectrophotometer, respectively. Anthracene was used as a standard in measuring the quantum yield of emission. 1H and 31 P{1H} NMR spectra were recorded at on either a Bruker ACF 300 spectrometer or a Bruker AMX500 spectrometer. All chemical shifts are quoted relative to SiMe4 (1H) or H3PO4 (31P). Variable temperature spectra were obtained by using a Bruker variable temperature unit B-VT2000 to control the probe temperature. The sample temperature is considered to be accurate to ±18C. Elemental analyses of the complexes were carried out in the microanalysis laboratory in the department of chemistry, the National University of Singapore. Synthesis of 1,8-difluoroanthraquinone A mixture of dried 1,8-dichloroanthraquinone (8.00 g. 28.8 mmol) and anhydrous cesium fluoride (16.00 g. 105.2 mmol) in thoroughly dried DMSO (35 ml) was stirred for 12 hours at 135 ºC under N2 atmosphere. After being cooled, the mixture was poured in ice-water from which the precipitate was filtered. The solids were washed with water (4×250 ml) and methanol (50 ml) and dried in vacuum. The crude material was chromatographyed on alumina with dichloromethane-hexane (2:1) as eluent. 4.22 g (60 %) of 1,8-difluoroantraquinone was obtained. 1H NMR (CDCl3, 300M Hz, δ/ppm) 8.15(d, 3JH,H = 7.6 Hz, 2H, H4, H5), 7.75(m, 2H. H3, H6), 7.50(m, 2H, H2, H7); 19F (CDCl3, 282.2M Hz, δ/ppm) -36 (s) which is similar as reference 1. Synthesis of 1,8-difluoroanthracene A mixture of 3.6 g (15.7 mmol) of 1,8- difluoroantraquinone, 21 g Zn dust, 40 ml H2O and 51 ml 28% aqueous NH3 was heated on a 188 steam bath with stirring for h at 75 ºC, then cooled and filtered. The residue and the filtrate were each extracted by CH2Cl2 and the combined CH2Cl2 extract was concentrated. A solution of the yellow solid in 190 ml i-PrOH and 17.4 ml of 12 M HCl was refluxed for hours and then concentrated and extracted between CH2Cl2 and aqueous NaHCO3. The organic layer was concentrated and the residue was recrystallized from i-PrOH to separate 3.0 g (95%) yellow solid. H NMR(CDCl3, 300M Hz, δ/ppm) 8.94(s.1H, H9). 8.47(s, 1H, H10), 7.80(d, 3JH,H = 8.4Hz, 2H, H4, H5). 7.45 (m, 2H, H3, H6), 7.18(dd, 3JH,H = 7.4Hz, 2H, H2, H7) [ABCX spin system with A, B, C =1H and X = 19F, 3JAB = 8.4 Hz, 3JBC = 7.4 Hz , 4JBX = 5.48 Hz , 3JCX = 10.9 Hz], 19F(CDCl3, 282.2M Hz) δ -46.2ppm(s). ESI-MS: m/z: 547 ([M+1]+, 100%) Synthesis of 1, 8-bis(diphenylphosphino)anthracene a) Sodium (1.25 g, 54 mmol) was added in 80ml dioxane (b.p.=101 ºC) and refluxed at 110 ºC. The sodium was molten and stirred vigorously to produce an emulsion of sodium in the dioxane. Chlorodiphenylphosphide (PPh2Cl, 3.6 ml, 20 mmol) dissolved in 20 ml dioxane was added slowly in the sodium solution to initiate the reaction. The addition finished in 30 min, then refluxed for another hours. The resulting yellow-green solution was stirred overnight at r.t. to prepare the PPh2Na for further use. 1,8-difluoroanthracene (1.0 g, mmol) dissolved in 20ml dioxane was transferred to the PPh2Na solution in 30min, then stirred at room temperature for another 30 min. Color of solution was changed from yellow to brown after refluxing the solution for another hours. When the solution was cooled down to r.t. gradually, ml CH3OH was added slowly and stirred for another half hour to remove the excess sodium and 20 ml deionzied water was added inside. The crude product was extracted by CH2Cl2 and the organic layer was concentrated to dryness. 1,8-bis(diphenylphosphino)anthracene was purified by column chromatography (SiO2, tolune/cyclohexane) to afford 1.307 g pale yellow solid, which is characterized by 1H NMR and 31P NMR. Yield is 51% related to the calculated product from 1,8-difluoroanthracene (1.0 g, mmol). b) At room temperature, 1-fluro-8-phenylphosphinoanthracene (1.3 g, 3.48 mmol) dissolved in 20 ml dioxane was add in PPh2Na dioxane solution for 30min, then stirred at room temperature for another 30 min. Color of solution was changed from yellow to brown after refluxing for 189 another hours. When the solution was cooled down to r.t. gradually, 5ml CH3OH was added slowly and stirred for another half hour to remove the excess sodium and 20ml deionzied water was added inside. The crude product was extracted by CH2Cl2 and the organic solvent was removed in vacuum. 1,8-bis(diphenylphosphino)anthracene chromatography(SiO2, toluene/cyclohexane) was purified by column to afford 0.909 g pale yellow solid, which is characterized by 1H NMR and 31P NMR. Yield is 48.5% related to the calculated product from 1-fluro-8-phenylphosphinoantracene (1.3 g, 3.48 mmol). 1H NMR (CDCl3, 300M Hz, δ/ppm): 9.79(t, JP,H = 5.1 Hz, 1H, anthracane H10), 8.44(s, 1H, H9), 7.97(d, JH,H = 8.4, 2H, anthracene H4,5), 7.25( m, 2H, anthracene H2,7), 7.03(dd, 2H, JH,H = 7.4Hz, anthracene H3,6), 7.25-7.22 (m, 20H, phenyl H). 31P (CDCl3, 121.5M Hz, δ/ppm): -14.63(s). 1-fluro-8-phenylphosphinoantracene Sodium (0.36 g, 15.6 mmol) was added inside 80 ml dioxane ( b.p.=101 ºC), then the solution was refluxed. The sodium was molten and stirred vigorously to produce an emulsion of sodium in the solvent. Chlorodiphenylphosphide (PPh2Cl, 1.05 ml, 5.83 mmol) in 20 ml dioxane was added dropwised at very slow rate to initiate the reaction. Then the mixture was refluxed for another h. The resulting yellow-green solution was stirred overnight at r. t. to prepare the PPh2Na for further use. 1,8-difluoroantracene (1.0 g, mmol) dissolved in 20 ml dioxane was transferred to the PPh2Na for 30 min, then stirred at room temperature for 30 min. Color of the solution was changed from yellow to brown after being refluxed for another hours. When the solution was cooled down to r.t. gradually, ml CH3OH was added slowly to remove the excess sodium and stirred for 30 min. and 20 ml deionzied water was added. The crude product was extracted by CH2Cl2 and further purified by column chromatography (SiO2, tolune/cyclohexane) to afford 1.27 g pale yellow solid as 1-fluro-8phenylphosphinoantracene. Yield(73%). 1H NMR(CDCl3, 300M Hz, δ/ppm): 9.30(d, JP,H = 4.4 Hz, 1H, antraphane H10), 8.45(s, 1H, H9), 7.97-7.10(m, 6H, anthrance H4,5, H3,6 and H2,7), 7.327.40(m, 10H, phenyl H). 31P(CDCl3, 121.5M Hz, δ/ppm) -16.1(s). Synthesis of Pt(DAP)Cl 4.1 a) A 180ml chloroform suspension of PtCl2(CH3CN)2 (0.129 g, 0.37 mmol) and 1,8- dis(diphenylphosphino)anthracene (0.202 g, 0.37 mmol) was refluxed for 20 hours. Insoluble 190 material was then removed by filtration and the filtrate was evaporated to ml and treated with excess diethyl ether to give yellow-green precipitates (0.169 g). Green crystals were grown in CH2Cl2/hexane. Yield (58.7 %). b) KPtCl4 (0.158 g, 0.38 mmol) and 1,8-bis(diphenylphosphino)antracene(0.208 g, 0.38 mmol) was mixed in 60 ml degassed CH3CN/H2O( ratio is 1:1) solution and heated at reflux for 18 hours. When the solution is cooled down to r.t. graduately, most of solvent was then removed by vacumn. The solution was extracted by CH2Cl2 and the organic portion was combined together. After dried by MgSO4, the solvent was reduced to ml in vacuum and treated with excess diethyl ether to give yellow-green precipitate (0.26 g). Yield(88.2%). C39H29PtCl3P2: Calcd (%). C, 54.27; H, 3.62; found (%). C, 54.35; H, 3.05; 1H NMR(CDCl3, 500M Hz, δ/ppm) 8.11(t, 5JPt,H = 2.4 Hz, 1H, H10), 8.35(d, JH,H = 8.1 Hz, 2H, H4,5), 7.95(m, 8H, phenyl H), 7.79(m, 2H, H2,7), 7.54(dd, JH,H = JH,H = 8.1 Hz, 2H, H3,6), 7.48-7.43(m, 12H, Phenyl H). 31 P{1H} NMR(121.5M Hz, CDCl3, δ/ppm): 39.8(s) (JPt,P = 2994.4 Hz). FAB MS: m/z: 776 ([M+1]+, 93%), 740.1([M-Cl]+, 100%). Synthesis of Pt(DAP)Br 4.2 and Pt(DAP)I 4.3 A mixture of 4.1 (0.10 g, 0.129 mmol) and excess KBr (0.5 g, 4.1 mmol) or KI (2g, 12.1 mmol) was stirred in 80 ml dichloromethane/methanol ( ratio is 1:1 ) at r.t. for 48 h. Yellowish solids were obtained after the solvent was evaporated. The solids were then extracted with dichloromethane. The yellow solution was concentrated to ml. Addition of excess diethyl ether to the solution precipitated the product as yellow solids. Crystals of both compounds were obtained from slow diffusion of hexane into a dichloromethane solution of the complexes. 4.2: for C39H29PtBrCl2P2, Calcd (%) C, 51.73; H, 3.23; found (%); C, 51.24; H, 3.44. 1H NMR (CDCl3, 300M Hz, δ/ppm): 8.38 (t, 5JPt,H = 2.4 Hz, 1H, anthracene H10), 8.10 (d, JH,H = 8.4 Hz, 2H, H4,5), 7.97-7.88 (m, 8H, phenyl H), 7.75 (m, 2H, H2,7), 7.51 (m, 2H, H3,6), 7.48-7.24 (m, 12H, phenyl H). 31P{1H} NMR (CDCl3, 121.5MHz, δ/ppm): 40.3(s) (JPt,P = 2968 Hz). ESI MS: m/z: 823 ([M+1]+, 93%), 4.3: for C39H29PtICl2P2. Calcd (%) C, 49.18; H, 3.06. found (%); C, 49.52; H, 3.32. 1H NMR (CDCl3, 300 MHz, δ/ppm): 8.44 (t, 5JPt,H = 2.4 Hz, 1H, anthracene H10), 8.11 (d, JH,H = 7.6Hz, 2H, 191 H4,5), 7.96-7.86 (m, 8H, phenyl H), 7.73(m, 2H, H2,7), 7.51 (dd, JH,H = JH,H= 7.6 Hz, 2H, H3,6), 7.48-7.25 (m, 12H, phenyl H). 31P{1H} NMR (CDCl3, 121.5M Hz, δ/ppm) 41.0ppm(s) (JPt,P = 2926 Hz). ESI MS: m/z: 867 ([M+1]+, 50%), 4.1 (0.22 g, 2.8×10-4 mol) and AgCF3SO3(0.07g, Synthesis of Pt(DAP)C≡CPh 4.4 2.8×10-4 mol)was stirred in a 100 ml CH3CN for 24 hours. The white AgCl precipitate was filtered and the yellow solution was transfer to the 50 ml CH3CN containing KOH (excess) and HC≡CPh (0.4 ml, 3.72 mmol). After stirring for 48 hours, the solvent was removed by evaporation and the solids were extracted with CH2Cl2. The solution was then filtered and evaporated to dryness. ml CH3OH was added and the brown precipitate was filtered and dried under vacuum (0.18 g). Yellow crystal was grown in CH2Cl2/hexane. Yield (63.4%) C46H32PtP2: Calcd (%) C, 65.55; H, 3.83; found (%); C, 65.38; H, 4.06;. 1HNMR (CDCl3, 300M Hz, δ/ppm) 8.34 (t, 5JPtH = 2.0 Hz, 1H, anthracene, H10), 8.10(d, JH,H = 8.2 Hz, 2H, H4,5), 8.01-7.97(m. 8H, phenyl H), 7.82(m. 2H, H2,7), 7.54(d, JH,H = 8.2 Hz, 2H, H3,6), 7.40-7.36 (m, 12H, Phenyl H), 7.20-7.14( m, 3H, Phenyl H), 7.06 (m,1H, Phenyl H). 31P{1H}NMR (CDCl3, 121.5M Hz, δ/ppm): 40.2(s) ( JPt, P=2883.8Hz). ESI MS: m/z: 845([M+1]+, 10%) Synthesis of Pd(DAP)Cl 4.5 A 150ml chloroform suspension of PdCl2(CH3CN)2 (0.119 g, 0.46 mmol) and 1,8-dis(diphenylphosphino)antracene (0.250 g , 0.45 mmol)was refluxed for 15 hours. Insoluble material was then removed by filtration and the filtrate was evaporated to ml. Addition of excess diethyl ether to the solution led to orange precipitates. Orange crystals of the product were obtained from CH2Cl2/hexane solution of the compound. Yield ( 88.2%); C46H32PdP2Cl, Calcd (%): C, 60.72; H, 3.65. found (%); C, 61.12; H, 3.72. 1H NMR(CDCl3, 300M Hz, δ/ppm): 8.29 (t, 5JPt, H = 2.7 Hz, 1H, anthracene, H10), 8.08(d, JH,H=8.4 Hz, 2H, H4,5), 7.88-7.77(m. 8H, phenyl H), 7.70(m, 2H. H2,7), 7.51(dd, JH,H = JH,H = 8.4 Hz, 2H, H3,6), 7.437.29(m. 12H, phenyl H). 31 P(CDCl3, 121.5M Hz, δ/ppm): 43.0(s). FAB MS: m/z: 687.87 ([M+1]+, 10%), 650.8 (PdDAP+, 60%) Steady-State Photolysis A LPS 300 SM xenon arc lamp controlled by model LPS 300SM switched mode as power supply in the range of 75 to 300 Watt was used as the light source in the photolysis. Light filter is used to control the wavelength for irradiation. The 192 incident light was focused by a lens. Photooxidation of NMR samples was carried out using xenon lamp with corresponding 300-500 nm or 600-800 nm filters. During the course of the photoreaction, the UV-vis absorption cell containing the samples was placed 35 mm away from the lamp. The UV-vis absorption changes were monitored by a Hewlett-Packard HP8452A diode array spectrophotometer and the concentration of 4.1 and 4.4 was estimated from the absorbance at 455.5 nm and 457 nm, respectively. The absorption of the photoproducts at that wavelength can be ignored compared with starting materials. The photoreaction proceeds with a quantum yield with 300-500 nm irradiations as determined by ferrioxalate actinometry according to the reported procedure.46 The quantum efficiency is 0.98 in the range of 300-500 nm for potassium ferrioxalate. The intensity of the incident light was of the order of 5.15×1017 proton/min or 1.42×10-8 einstein/s at 81Watt, 300-500 nm wavelength. In order to detect the quantum yield of photolysis of 4.1 and 4.4, all the process for both standard and sample must be obtained under the same instrumental conditions. Compound 4.1 and 4.4 was dissolved in CHCl3 and placed in a quartz cell, which was placed 3.5 cm from the light source. During the process, the light beam passed through a 300-500 nm light filter and focused onto a 1×1 cm quartz cell that contained ml of sample solution. Samples were exposed to light and the change in the UV visible absorption spectrum was monitored. During the photooxidation procedure, the solution was contacted with air atmosphere by shaking or stirring. The quantum yield of photolysis is 5.0% for 4.1 and 7.9% for 4.4 based on the reported method43 at 81 Watt, 300-500 nm wavelengths. 4.6: 4.1 (0.05 g, 0.067 mmol) was dissolved in CHCl3 (A.R.) and irradiated by fumehood light for 51-118 hours. After filteration, all the solvent is removed by vacuum. Violet block crystal is grown by slowly diffusion CH3CN. Yield is 50% based on the crystal grown from the crude product. C46H32PtP2 Calcd (%): C, 65.55; H, 3.83. found (%); C, 65.38; H, 4.06; 1H NMR(CDCl3, 500M Hz): δ = 8.29(d, 2H, JH,H = 7.4 Hz, H4,5), 7.88(m, 4H, phenyl H), 7.82(m, 4H, phenyl H), 7.71(m. 2H, H2,7), 7.60(dd, JH,H = JH,H = 7.4Hz, 2H, H3,6), 7.48-7.43(m, 12H, Phenyl H), 31 P{1H} NMR (CDCl3, 121.5 MHz, δ/ppm): 39.9ppm(s), (JPt,P= 3171 Hz). ESI MS: m/z: 851([M+1]+, 100%). 193 4.7 4.4 (0.05 g, 0.067 mmol) was dissolved in CHCl3(A.R) and irradiated by fumehood light for 81 hours. After filtration, all the solvent was removed by vacuum. Colorless block crystal was grown by slowly evaporation of dioxane. Yield (30%). 1H NMR(CDCl3, 500M Hz, δ/ppm) 8.03(d, JH,H = 7.4 Hz, 2H, anthracene H4,5), 7.85-7.40(m, 20H, phenyl H), 7.30(dd. 2H, JH,H = JH,H = 7.4 Hz, anthracene H2,7), 7.05-6.99(m, 6H, anthrance H3,6 and Phenyl H), 6.76(m, 2H. phenyl H), 3.70(s, 16H, dioxane H), 3.09(s, 1H, OH). 31P{1H} NMR (CDCl3, 121.5 MHz δ/ppm): 21.3ppm(s) ( JPt, P= 2816 Hz). ESI MS: m/z 872([M-OH]+, 92%). 4.8 4.4 (0.05 g, 0.067 mmol) was dissolved in CHCl3 (A.R) and irradiated by fume-hood light for 81 hours. After filtration, all the solvent is removed in vacuum. Colorless block crystal was grown by slowly diffusion CH2Cl2/CH3OH. Yield (20%). 1H NMR(CDCl3, 500M Hz, δ/ppm) 8.03(d, 2H, JH,H = 7.4Hz anthracene H4,5), 7.85-7.41(m, 20H, phenyl H), 7.29(dd. 2H, JH,H = 5.1 Hz anthracene H2,7), 7.05-6.98(m, 6H, anthrance, H3,6 and Phenyl H), 6.76(d, 2H, JH,H = 7.4 Hz, phenyl H), 2.40(s, 3H, CH3). 31P{1H} NMR (CDCl3, 121.5 M Hz, δ/ppm): 21.3 ppm( JPt, P= 2826 Hz). FAB MS: m/z: 903.8([M+1] +, 5%), 888.8 ([M-CH3]+, 23%), 871.9([M-CH3OH]+, 88%), 770.9 ([M-CH3OH-C≡C-Ph]+, 32%). 4.9 4.1 was dissolved in CDCl3 (C= 6×10-4 M) in volumetric flask and kept in darkness for 24 hours. The 1H NMR and 31 P NMR would totally change. All the solvent was removed by vacuum. Red crystal was grown by slowly evaporation of acetonitrile solution. 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Organometallics 1984, 3(10), 1479. 199 [...]... 380.5(7.17), 40 1.5(6.29) 238(52.33), 279( 64. 32), 379 (2.11), 42 9 (6 .45 ), 45 4 (7.15), 516(0.038), 643 (0.018), 703(0.027) 242 (51.33), 280 ( 54. 12), 336 (4. 621), 379 (2.77), 42 8 (6.85), 45 4 (7.61) 244 .5 (6.19), 282 (53.13), 344 (7.91), 377 (4. 70), 43 0 (8.70), 45 4 (9.76) 280(59.23), 368 (12.08), 40 1(3.81) ,43 1 (8.19), 45 8 (8.98) 277 (53.51), 315 (7.67), 3 74 (1.91), 393 (3.23), 41 4 (5.397) ,43 9 (5.56)   Compounds... Coefficient (M cm ) 5.0x10 4 4.0x10 4 3.0x10 4 2.0x10 4 1.0x10 0.0 250 300 350 40 0 45 0 500 550 Wavelength (nm) Figure 4. 23 UV-vis absorption spectra of Pt(DAP)X( X=Cl, Br, I) in CH2Cl2 at 298 K 126 4 4 5x10 -1 -1 Extinction Coefficient (M cm ) 6x10 4 4x10 4 3x10 4 2x10 4 1x10 0 300 40 0 500 Wavelength (nm) Figure 4. 24 UV-vis absorption spectrum of 4. 4·CH2Cl2 in CH2Cl2 at 298 K 4 6x10 4 -1 -1 Extinction Coefficient... (Figure 4. 25) It is reasonable as the mixing between Pd and anthracenyl orbitals should be weaker as the 4d orbitals of the Pd are lower in energy The UV-vis absorption data of the complexes are listed in Table 4. 6 Table 4. 6 UV-vis absorption bands for free DAP and complexes 4. 1 -4. 5 measured in CH2Cl2 4. 2•CH2Cl2 4. 3•CH2Cl2 4. 4•CH2Cl2 4. 5•CHCl3 λ/nm ( × 10-3 M-1cm-1) 229(29.92), 266(71.65), 362 (4. 64) , 380.5(7.17),... of DAP resembles that of anthracene which exhibits two absorption bands at 255 nm and 358 nm 4 6x10 4 5x10 4 4x10 4 3x10 4 2x10 4 1x10 4 -1 -1 4 7x10 Extinction Coefficient (M cm ) 8x10 0 250 300 350 40 0 45 0 500 Wavelength (nm) Figure 4. 22 UV-vis absorption spectrum of DAP in CH2Cl2 at 298 K The electronic absorption spectra of Pt(DAP)X (X = Cl Br and I) are depicted in Figure 4. 23 The spectra are similar,... 166.90 (4) 178.00(10) 95.57(3) 97.18(3) 118.0 (4) 121.0(3) 121.0(3) 126.9 (4) 112.1(3) 127.0(3) Table 4. 3 Selected bond length(Å) and angles(deg) of 4. 3·CH2Cl2 Bond Lengths Pt(1)-C(9) Pt(1)-P(2) Pt(1)-P(1) Pt(1)-I(1) P(1)-C(1) P(2)-C(8) C(9)-C(13) C(9)-C(11) C(1)-C(11) C(11)-C(12) C(13)-C( 14) C(8)-C(131) 2.015(5) 2.2739( 14) 2.27 84( 14) 2.6 645 (5) 1.820(5) 1.821(3) 1 .40 7(7) 1 .40 8(7) 1 .41 8(7) 1 .44 1(7) 1 .43 9(7)... 4. 2·CH2Cl2 and 4. 3 are similar with 4. 1 In ESI-MS and FAB-MS, no molecule peak could be observed in 4. 2·CH2Cl2 and 4. 3·CH2Cl2 109 a) b) Figure 4. 9 ORTEP diagrams of 4. 2·CH2Cl2 showing (a) the top view and (b) the side view 110 All three Pt(II) complexes have similar structure and π-π interaction modes Figure 4. 9 show 4. 2·CH2Cl2 are stacked in a head-to-tail fashion in the dimer from top view and side... Compare to other Pt(II) complexes, 4. 3·CH2Cl2 has weaker C•••H-π interaction 111 a) b) Figure 4. 10 ORTEP diagrams of 4. 3·CH2Cl2 showing (a) the top view and (b) the side view 112 Figure 4. 11 and 4. 12 show unit cells which contain head-to-tail dimers of 4. 2·CH2Cl2 and 4. 3·CH2Cl2 Face-to-face π-π stacking is clearly observed Figure 4. 11 Crystals packing of 4. 2·CH2Cl2 Hydrogen atoms and solvent are omitted... Coefficient (M cm ) 5x10 4 4x10 4 3x10 4 2x10 4 1x10 0 250 300 350 40 0 45 0 500 550 Wavelength (nm) Figure 4. 25 UV-vis absorption spectrum of 4. 5 in CH2Cl2 at 298 K 127 The red-shift of the ligand centered π→π* transition in the Pt(DAP) complexes is due to the mixing of the metal p-orbitals and the anthracenyl π-orbitals The molecular orbitals for DAP are similar characteristic orbitals as anthracene with little... C(3)-C (4) C (4) -C(12 C(15)-C(16) 2.019(3) 2.029(2) 2.2638(6) 2.2638(6) 1 .40 9(3) 1 .41 4(3) 1 .43 1(3) 1 .43 5(3) 1.3 64( 3) 1 .41 6 (4) 1.361 (4) 1 .42 0(3) 1.203 (4) Bond angles C(15)-Pt(1)-C(9) C(15)-Pt(1)-P(1) C(9)-Pt(1)-P(1) C(15)-Pt(1)-P(2) C(9)-Pt(1)-P(2) P(1)-Pt(1)-P(2) C(1)-P(1)-Pt(1) C(8)-P(2)-Pt(1) C(11)-C(9)-C(13) C(11)-C(9)-Pt(1) C(13)-C(9)-Pt(1) C(16)-C(15)-Pt(1) 179.60(9) 96.26(7) 83.35(6) 97 .43 (7) 82.96(6)... 1 .43 9(7) 1 .42 1(7) Bond angles C(9)-Pt(1)-P(1) C(9)-Pt(1)-P(2) P(2)-Pt(1)-P(1) C(9)-Pt(1)-I(1) P(1)-Pt(1)-I(1) P(2)-Pt(1)-I(1) C(11)-C(9)-C(13) C(11)-C(9)-Pt(1) C(13)-C(9)-Pt(1) C(7)-C(8)-P(2) C(11)-C(1)-P(1) C(2)-C(1)-P(1) 83.58(15) 83.52(15) 166.86(5) 178.25( 14) 95.66 (4) 97.30 (4) 118 .4( 4) 120.8 (4) 120.8 (4) 121.7(5) 112.1 (4) 126.2 (4) Similar to complex 4. 1·CH3CN, the Pt(II) centers in 4. 2·CH2Cl2 and 4. 3·CH2Cl2 . 166.86(5) 178.25( 14) 95.66 (4) 97.30 (4) 118 .4( 4) 120.8 (4) 120.8 (4) 121.7(5) 112.1 (4) 126.2 (4) Similar to complex 4. 1·CH 3 CN, the Pt(II) centers in 4. 2·CH 2 Cl 2 and 4. 3·CH 2 Cl 2 . C(2)-C(3) C(3)-C (4) C (4) -C(12 C(15)-C(16) 2.019(3) 2.029(2) 2.2638(6) 2.2638(6) 1 .40 9(3) 1 .41 4(3) 1 .43 1(3) 1 .43 5(3) 1.3 64( 3) 1 .41 6 (4) 1.361 (4) 1 .42 0(3) 1.203 (4) C(15)-Pt(1)-C(9). C(9)-C(13) C(13)-C(8) C(13)-C( 14) C(12)-C(7) C(1)-C(11) 1.991(3) 2.26 64( 9) 2.2705(9) 2.39 14( 9) 1.809 (4) 1.803 (4) 1 .41 1(5) 1 .41 3(5) 1 .43 2(5) 1 .43 5(5) 1 .43 5(5) 1 .44 1(5) C(9)-Pt(1)-P(2) C(9)-Pt(1)-P(1)