Luminescent metal complexes containing naphthalene and anthracene units 1

Chapter Structural and Spectroscopic Properties of d10 Metal Thiolates 1.1 Introduction Metal-thiolate complexes have been known since the beginning of coordination chemistry. However, there is an increasing interest in the study of this species in the last two decades which is due to a diversity of factors. First, metal-thiolate complexes are of great importance, mainly because of the wide occurrence of cysteine thiolate in the coordination sphere of many metal ions in various metalloproteins. On the practical side, there is a growth in the utilization of metal thiolates in medicine. For example, gold thiolates compounds are used in the treatment of arthritis or cancers. In addition, volatile metal-thiolates are common starting materials for chemical vapor deposition of layers of metals or sulfides form vapor phase. But most important, the chemical and physical properties of metal-thiolate complexes are very rich: there are numerous studies of the structures, reactivity, electronic spectroscopy and electrochemistry of metal-thiolates continues to attract the attention of chemists. There are many aspects of metal thiolate chemistry but we are particularly interested in the photophysical, spectroscopic and structural properties of polynuclear d10 metal thiolates. As an emerging class of inorganic materials, the polynuclear d10 metal complexes display intriguing structural diversity and interesting physical properties and chemical reactivity. Metals of a d10 electronic configuration commonly form complexes with coordination numbers varying from two to four and accordingly with a variety of geometries. For example, linear, trigonal planar and tetrahedral copper(I) complexes are known. Accordingly, polynuclear d10 metal complexes are expected to display even greater structural complexity. While metal-ligand interactions play a key role in defining the structures of the d10 polynuclear complexes, the importance of d10-d10 metal-metal interactions cannot be underestimated. In principle, the interaction between the closed-shell d10 metal centers would not lead to any chemical bonding. However, due to configuration mixing of the filled nd orbitals with the empty orbitals derived from higher energy (n+1)s and (n+1)p atomic orbitals, there is a weak attraction between the metal centers (Figure 1.1). This interactions, known as metallophilicity, have been widely observed in polynuclear Cu(I), Ag(I) and Au(I) complexes and have a determining effect on the structures of the complexes. pσ∗ Figure 1.1 n+1pz n+1pz dσ∗−pσ∗ mixing pσ LUMO dσ∗−>pσ transition HOMO dσ∗ ndz2 ndz2 dσ−pσ mixing dσ In addition to the structural effect, the d10-d10 metal-metal interactions also have pronounced effect on the electronic spectroscopy of the compounds. Because of the metal-metal interactions, the highest occupied molecular orbital (HOMO) of a d10-d10 bimetallic complex is the filled dσ* orbital and the lowest unoccupied molecular orbital (LUMO) is the empty pσ orbital. The lowest energy fully allowed electronic transition is 1dσ*→pσ transition. Due to the strong spin-orbital coupling, especially for heavy metals like Ag and Au, the transition would lead to the formation of the spin-forbidden 3dσ*1pσ1 excited state. Previous studies on many binuclear d10-d10 AuI-AuI, Pt0-Pt0, Pd0-Pd0, AgI-AgI and CuI-CuI showed that the 3dσ*1pσ1 is emissive and the complexes can display long-lived (µs) phosphorescence in solution or solid state. As an electron is promoted from an antibonding dσ* to a bonding pσ orbital, the bond order between the d10 metal centers increases the 3dσ*1pσ1 excited state, leading to a contraction of the metal core in the clusters. In combination with different ligands, the ground state and excited state electronic structures of the polynuclear d10 complexes could be altered significantly as the involvement of ligand orbitals in the frontier orbitals cannot be neglected. In accord, a number of luminescent polynuclear d10 metal complexes have been suggested to emit from an excited state other than that of a pure metal-centered origin. Because of the completely filled d-shell, there is no ligand field d-d transition in the polynuclear d10 metal complexes. However, depending on the nature of the ligands coordinating to the metal centers, the complexes can display low-energy chargetransfer transitions. In general, there are three types of intramolecular charge-transfer transitions, which are classified according to the nature of the orbitals involved: (i) metal-to-ligand-chargetransfer (MLCT), (ii) ligand-to-metal-charge-transfer transition (LMCT) and (iii) ligand-toligand-charge-transfer transition (LLCT). MLCT transitions occur with a transfer of electron from a metal-centered orbital to an empty orbital which is predominantly ligand-based orbital. Such transitions tend to be prominent in systems composed of an easily oxidized metal and a ligand containing a low energy acceptor orbital. As d10 metal ions are considered electron-rich, it can display low-energy MLCT transition if the ligands contain low-lying empty orbitals. [Cu(diimine)2]+ (where diimine denotes the derivative of 1,10-phenanthroline or 2,2’bipyridine) complexes exhibited strong absorption in the visible region, which was assigned as metal-to-ligand charge-transfer (MLCT) transition where the electron was promoted from a 3d orbital of copper to a low-lying π* orbital of the ligand (Figure 1.2). Because the emission intensity varied with the temperature, therefore emission originated from at least two different excited states. Kirchloff et al. proposed that the two states, separated by about 1800 cm-1, represented the singlet and triplet spin states derived form the lowest energy MLCT state.7e and this result was analysized by detailed group theoretical assignments. 7k 1MLCT has higher energy and greater radiative rate constant compared with 3MLCT. Later short-lived emissions from copper(I) bis-(diimine) compounds were examined using a time-correlated single photon counting (TCSPC) technique with picosecond time resolution by Zainul.8 On 400nm laser excitation of [Cu(dmphen)2]+ in CH2Cl2 solution, prompt 1MLCT fluorescence with a quantum yield of (2.8 ± 0.8)×10-5 was observed. [Ag(phen)(CN)]·(phen) (phen = 1,10-phenanthroline) also showed both metal-to-ligand charge transfer (MLCT) mixed with the cyanide-to-ligand charge transfer and [πL-πL*] of the uncoordinated phen species in the solid state. (Figure 1.3) Figure 1.2 N + + RR N N Cu N N Cu N N N RR R=CH3, C4H9 Figure 1.3 N Ag C N N LMCT transitions originate from an electron transition which involves a filled ligand orbital and an empty metal orbital. Usually metal complexes which contain electron-rich ligands and/or high-valent metal center would display low-energy LMCT transition. Especially, ligands which contain more than one lone-pair of electrons would have a lower LMCT energy because the lone-pair electrons are higher in energy. Accordingly, many complexes containing chalcogenides (S2-, Se2-) and thiolates (SR-) show low energy LMCT absorption bands in their electronic spectroscopy. Notably LMCT transition is the lowest energy allowed transitions for many mononuclear and polynuclear d10 metal complexes which contain sulfides S2- or thiolates ligands. Some of the complexes are photoluminescent and the emission is derived from the LMCT excited states. For example [Cu6(µ-P^P)4(µ3-SePh)4](BF4)2 (P^P=dppm, 1; (Ph2P)2NH), 2) (Figure 1.4).10 The absorption shoulders at ca. 290 nm with tails extending to ca. 400 nm were likely to arise form chalcogenolate ligand-centered and chalcogenolate–to-copper charge-transfer (LMCT) transitions. Excitation of degassed acetone solution of and at λ > 350 nm produced a low energy emission band at 626 and 700 nm, respectively. Such emission was assigned to [PhSe—Cu6] LMCT transition mixed with copper-centered d-s state. Figure 1.4 Ph2 P Ph2 P 2+ HN Cu Ph2P Se PPh2 Se Cu Se Cu Cu Ph2P Cu Cu P Ph2 Se PPh2 P Ph2 Ph2 P Ph2 P Cu Ph2P Se PPh2 Cu Cu Ph2P HN NH Se Cu Se 2+ Cu Cu Se PPh2 P NH Ph2 P Ph2 Phosphinidene group, like unsubstituted chalcogenide, is also a good σ-donor. [Cu4(µdppm)4(µ4-PPh)](BF4)211 (Figure 1.5) showed low energy absorption band at 466 nm which was likely to be originated for the [P(phosphinidene)→Cu] ligand–to-metal charge-transfer (LMCT) transition. Excitation in the solid state and in fluid solution at λ= 500 nm resulted in intense longlived red luminescence. The observed lifetime in the microsecond range indicated the spinforbidden nature of emission, which was tentatively assigned to be originated predominantly from the triplet ligand–to-metal charge-transfer (LMCT) transition [P(phosphinidene)→Cu]. Figure 1.5 2+ Ph P P P P Cu Cu Cu P Cu P P P P Au12(µ2-dppm)6(µ3-S)4](PF6)4,12 showed absorption at 332 nm. Excitation with wavelength λ > 350nm produced a long-lived orange-red emission in solid state and a green emission in solution at room temperature respectively, which was assigned to 3[LMCT] S-Au mixed with metal-centered (ds/dp) states modified by AuI-AuI interaction. (Figure 1.6) Figure 1.6 4+ Ph2P Ph2 P Au Au Ph2P Ph2P Au Au Ph2P Au PPh2 Au S S S S Au Ph2P Au Ph2 P Au Au Au Au PPh2 PPh2 P Ph2 PPh2 Au12(µ2-dppm)6(µ3-S)4](PF6)4 LLCT transition is commonly observed in complexes which contain an electron-rich ligand and a ligand which possesses low-lying empty orbitals. If the filled orbitals (lone-pair) of the electron-rich ligand is higher in energy than the metal orbitals and the low-lying empty orbitals of the other ligand are more stabilized than the empty metal orbitals, then the lowest energy electron transition would involve a transfer of electron from the filled orbital of the electron-rich ligand to the empty orbital of the other ligands. Compared with vast examples of MLCT and LMCT, there are only few example of d10 metal complexes with LLCT emission. Most examples are Zn(II), Pt(II) and Pd(II) complexes.13 The LLCT absorption band energy is almost insensitive to the metal. In the (hydrotris- (pyrazolyl)borato)(triphenylarsine)copper(I) [CuTpAsPh3] (Figure 1.7).14 The spectrum of the arsine complex contained low-energy bands (with a band maximum at 606 nm in emission and a weak shoulder centered at about 400 nm in absorption). The lowest energy electronic transition was assigned to ligand to ligand charge transfer (LLCT) with some contribution from the metal. This assignment was consistent with molecular orbital calculations that showed the HOMO to consist primarily of σ orbitals on the Tp ligand (with some metal orbital character) and the LUMO to be primarily antibonding orbitals on the AsPh3 ligand (also with some metal orbital character). The absorption shoulder showed a strong negative solvatochromism, indicative of a reversal or rotation of electric dipole upon excitation, and consistent with a LLCT. The complex (dmp)CuBH4 (dmp=2,9-dimethyl-1,10phenanthroline) displayed a long-wavelength absorption at λmax = 465 nm which was assigned to a BH4--dmp-ligand-to-ligand charge transfer (LLCT) transition. In solid state, the LLCT state was emissive at λmax=626 nm. 15 Figure 1.7 H N N N N Cu As B N N Cu N N H H 1.2 H B H The Structural and Spectroscopic Properties of d10 Au(I), Ag(I) and Cu(I) thiolate Chacogenides are well known to possess a variety of bonding characteristics and there have been a number of polynuclear d10 metal complexes with thiolates as the bridging ligand. They commonly act as a µ2-, µ3- and µ4- bridging ligand but a µ8- bridging mode has been observed. A large number of Au complexes with thiolate ligands have been reported compared with other d10 metal complexes The mutual attraction between gold(I) center is easier to form compared with silver(I) or copper(I). Gold(I) thiolates are often photoluminescent at room temperature and the emission properties can be strongly affected by the presence of aurophilic Au…Au interactions and nature of thiolates.16 Luminescence has thus become an important diagnostic tool for aurophilicity. A remarkable example of the luminescence of a gold(I) compound which showed strong solvent dependence was published by Che et al.17 The quenching of the luminescence of the simple dinuclear gold(I) quinoline-8-thiolate in polar solvents such CH3CN and CH3OH was attributed to an equilibrium between two forms A and B complexes. A transfered to B in the polar solvent (Figure 1.8). Figure 1.8 PPh3 Ph3P Au A PPh3 PPh3 Au S N + Au K + Au S N B A trinuclear complex [(8-QNS)2Au(AuPPh3)2]·BF4 (8-QNS= quinoline-8-thiolate), with intramolecular gold(I)-gold(I) distances of 3.0952(4) and 3.0526(3) Å, was aggregated to form a novel hexanuclear supermolecule, {[(8-QNS)2Au(AuPPh3)2]}2·(BF4)2, via a close intermolecular gold(I)-gold(I) contact of 3.1135(3) Å.18 The compound also showed interesting spectroscopic and luminescence properties dependent on the solvent polarity. It emitted at ca. 440 and 636 nm in CH2Cl2 and only at ca. 450 nm in CH3CN. The long-lived emission at ca. 636 nm in CH2Cl2 was quenched by polar solvents such as CH3CN and CH3OH, which was suggested to be related to the presence or absence of gold(I)-gold(I) interactions due to scrambling of the [AuPPh3]+ units ( Figure 1.9). Figure 1.9 + + N Ph3P N PPh3 S Au Au Au S Ph3P N Au S Au Au Ph3P S A N B This unique behavior can be exploited in the development of sensing materials for different analytes. For example, a dinuclear gold(I) crown-ether complex which showed a high selectivity towards potassium ions. 1, Dinuclear gold(I) crown-ether complexes [Au2(P^P)(SB15C5)2] {P^P = dppm or dcpm (bis(dicyclohexylphosphino)methane), SB15C5=4'sulfanylmonobenzo[15]-crown-5} were found to form 1+1 adducts with potassium ions with log K values of 3.4 and 4.0, respectively. This indicated that one potassium ion was sandwiched between the two benzo-15-crown-5 rings of the dinuclear Au(I) molecule (Figure 1.10), which has also been confirmed by electrospray-ionization mass spectrometric (ESI-MS) studies. The emission spectrum of the former showed a drop in intensity at ca. 502 nm, with the concomitant formation of a long-lived emission band at ca. 720 nm (to = 0.2 ms) upon addition of potassium ion . Such a change in emission spectral traces was absent in the crown-free analogues. Thus, it was likely that the binding of K+ brings the two gold(I) centers in close proximity to each other, resulting in some weak Au…Au interactions. These intramolecular Au···Au interactions were then reported by the emission properties of the complexes. The low-energy emission band has been proposed to arise from a LMMCT [RS2 - Au2] excited State. 10 bonding between the gold atoms of the sulfonium group. At either end of the phenylene centerpiece, the gold atoms of two neighboring dication formed tetranuclear units with short AuAu distance. Figure 1.21 Tol3P PTol3 Au 2+ Au S S Au Au PTol3 Tol3P Ag dithiolate complexes and copper dithiolate complexes show similar structure but Ag has ability to form huge cluster and polymer. A neutral, tetranuclear silver(I) compounds, [Ag4(dppm)4(S2CC(CN)P(O)(OEt)2)2]](PF6) ( Figure 1.22) 37 was obtained from the reaction of Ag2dppm2(CH3CN)2(PF6)2 and K2S2CC(CN)P(O)(OEt)2. 1,1-dithiolate ligand displayed a tetrametallic tetraconnective (µ 2-S, µ 2-S) bridging. The Ag-Ag distance was 2.9827 Å. Figure 1.22 O O P O N C P P S Ag Ag P P S P S P Ag P Ag P S O N P O O 20 Ag4(µ-dppm)4(µ4-i-mnt)2 (Figure 1.23) is also a tetranuclear complex with a silversilver separation of 3.376(2)Å and the four silver atoms form a distorted square plane bridged by four dppm and two i-mnt (S,S-C=C(CN)2) ligands. Each silver atom is coordinated by two phosphorus and two sulfur atoms in a distorted tetrahedral environment.38 Figure 1.23 Ph2P PPh2 Ag N N Ph2P S N Ag Ph2P PPh2 S S Ph2P Ag N S Ag PPh2 PPh2 Another kind of tetranuclear silver in [Bu4N]2[Ag4(i-mnt)4],39 four silver atoms located at the vertices of a slightly distorted tetrahedron. Four i-mnt groups acted as tridentate ligand. A sulfur atom of each ligand coordinated to only one silver atom with the other S atoms bridges across the Ag3 triangle to two adjacent silver atoms. The Ag-Ag distances were in the range of 2.943(2) Å to 3.045(2) Å (Figure 1.24). 21 Figure 1.24 N N 4- C C C C S S Ag S N C C C N C S Ag Ag Ag S S S C C N C C N S C C C N C N A novel pentanuclear silver complex, [Ag5(dppm)4(S2CC(CN)P(O)(OEt)2)2]](PF6) 37 was got with a short Ag-Ag distance of 2.9827 Å ( Figure 1.25). - Figure 1.25 P Ag O P S recent [Ag4(SCH2C6H4CH2S)3]2-, S Ag Ag decade, 40a many O O P P N the O C P S O In S Ag P P O N P Ag P P polysilver(l)-thiolate [Ag9(SCH2C6H4CH2S)6]3-, 40b complexes, such [Ag6(i-mnt)6]6- (Figure 1.26), as 40d [Ag8(i-mnt)6]4- {i-mnt: S2C=C(CN)2)} (Figure 1.27) 40c and [Ag11(µ5-S)(S2CNEt2)9]40e have been reported. 22 Figure 1.26 N N C C S C S Ag N C C N C C S S S C N C C C S Ag Ag Ag Ag S S C C S Ag S N C C C C S 6- N N C C N C S C C N C C N N Figure 1.27 N N C 4- C N C C C S N N C C S C S S C C N Ag Ag Ag C S Ag Ag Ag S C S S Ag N C S Ag S C C C C C C C N N S S C N C C N C N In nonanuclear complex,41 (PPh4)3Ag9(SCH2CH2S)6, eight silver atoms formed a cubanelike metal skeleton with a further silver atom in the center( Figure 1.28). 23 Figure 1.28 S 3- S Ag Ag S S S Ag S Ag Ag Ag S Ag Ag S S Ag S S S H Four kinds of tetracopper clusters were reported. They had a common feature that a tetranuclear core inside and copper-copper interaction existed. In [Me4N]2[Cu4(C8H6S8)3] (Figure 1.29), 42 three dithiolate ligands, 2-[4,5-bis(methylsulfanyl)-1,3-dithiol-2-ylidene]-4,5-bis(2- cyanoethylsulfanyl)-1,3-dithiole, connected tetrahedral Cu4 cluster. The Cu-Cu bonds ranged 2.684(2)-2.739(2) Å. Such similar tetranuclear core was also observed in [Ph4P]2[Cu4(SCH2CH2S)3]. 41 Figure 1.29 S S S S 2- S S S S S Cu C S Cu S S S S S S S Cu SH S S S S S S 24 Two neutral, tetranuclear copper(I) compounds, [Cu4(dppm)4(S2CC(CN)P(O)(OEt)2)2]](PF6)2 and Cu4(dppm)3(OPPh2CH2PPh2)[S2CC(CN)P(O)(OEt)2]2, ( Figure 1.30) 37b was isolated from the same reaction of Cu2dppm2(CH3CN)2(PF6)2 and K2S2CC(CN)P(O)(OEt)2. 1,1-dithiolate ligand displayed a tetrametallic tetraconnective (µ 2-S, µ 2-S) bridging. Figure 1.30 O O P O N O O P N C C P P S Cu Cu P P S P S P Cu P Cu P P P Cu S O P S Cu P S O S P Cu P Cu P P S O N O P O O N P O O In [(Bu4N)]4[Cu4(i-mnt)4] (Figure 1.31),43 the anion revealed discrete units of four copper atoms, at the vertices of a distorted tetrahedron. With four i-mnt groups acting as ‘tridentate’ligand, a sulfur atom of each ligand coordinated to only one copper atoms with the other S atoms bridges across the Cu3 triangle to two adjacent copper atoms. So that each copper atom was in an approximately trigonal geometry with an almost planar arrangement of the three sulfur atoms coordinated to it. The Cu-Cu distances associated with the copper atoms bridged by the sulfur atoms bond to C range from 2.718 to 2.725 Å. The remaining Cu-Cu distances ranged from 2.814-2.825 Å. 25 Figure 1.31 4- SS S Cu S Cu Cu S S Cu S S Except these, Cu4(µ-dppm)4(µ4-i-CS3)2 (Figure 1.32) was a tetranuclear complex which had four copper atoms are in a square arrangement. Copper-copper distance was 3.305(6) and 3.32(6) Å separately. Each edge was doubly bridged by a dppm ligand and a sulfur atom form a CS32- anion.44 Figure 1.32 Ph2 P Ph2 P Cu S S S Ph2P Cu Cu Ph2P PPh2 S S S PPh2 Cu P Ph2 P Ph2 [Cu5(dppm)4(S2CC(CN)P(O)(OEt)2)2]](PF6) (Figure 1.33), a novel pentanuclear copper complex contained a tetradentate ligand bridging mode.37b An unprecedented tetrametallic hexaconnective coordination pattern, η3(µ2-S-µ3-S’-O) was revealed. Compared with same 26 structure of [Ag5(dppm)4(S2CC(CN)P(O)(OEt)2)2]](PF6)2. Copper atoms were three-coordianted and the silver ones are four-coordinated. Figure 1.33 + N P P P Cu P O S P N In [(Bu4N)]6[Cu6(s,i-MNT)6], Cu 43 O C P O S Cu S O P O Cu S P P O Cu P the Cu6S12 core were formed by connected 12 sulfur atoms of six dithiolate ligand with six Cu(I) atoms which were almost on a same plane with a deviation of 0.172 Å. As shown in Figure 1.34, there were three idealized octahedron cages formed by the S atoms. The central octahedron which was made form the six bridging sulfur atom was surrounded by another octahedron produced by the six catenated sulfur atoms. The third octahedrom of S atoms coordinated to Cu(I) was twisted relative to the other two. 27 Figure 1.34 N 6- N N S N S Cu S N S Cu S S N S Cu Cu S Cu S Cu S N S N S N N N N In Cu8(i-mnt)64- (Figure 1.35), each sulfur atom of six bidendate ligands bridged an edge of the Cu8 cube in such a way that the twelve sulfur atoms described as a distorted icosahedron.45 The S…S vector of each individual dithionate ligand lay perpendicular to one of the faces of the cube. Consequently, the whole cluster architecture exhibited the idealized Th symmetry. Figure 1.35 R 4S S Cu S Cu Cu Cu S R R Cu S Cu Cu Cu S S S R 28 1.3.1 Objective of Sudy Previous introduction reflects a rapidly growing interest in research of structure and spectroscopy of d10-thiolates complexes. Closed-shell interactions exist between the metal centers of complexes of d10 metal. These interactions, known as metallophilicity, have been widely observed in polynuclear Cu(I), Ag(I) and Au(I) complexes and have a determining effect on the structures of the complexes. The effects of 5d10-5d10 interactions on structure and bonding of such complexes are obvious and has the same order of magnitude as the strength of a typical hydrogen bond. For each Au…Au bond, close shell attractions are typically in the range 711kcal/mol.46 It appears that weak attractive forces between metal atoms or cations with seemingly saturated electron configurations play an important role in determining the configuration, conformation, and oligomerization of complexes. Since sulfur can act as good σdonors and capable of displaying a great diversity of structure and bonding modes. Thiolate anions are capable of binding two or three Cu(I), Ag(I) or Au(I) units to form species which contain metal-metal interaction. The presence of metallophilic contacts may be recognized not only from short metal(I)metal(I) distances and novel structural features, but also intriguing electronic absorption and luminescence properties. It has become clear that the gold(I)-gold(I) bonding interaction is responsible for the relevant transitions, and luminescence has thus become an important diagnostic tool for aurophilicity. This kind of luminescent gold(I) and copper(I) compounds hold great potential for analytical applications. Figure 1.36 NaBH4/LiAlH4 O2 S S SH SH NS2H2 29 In the present work, we intent to investigate the photophysics, photochemistry and structure properties of d10 metal-dithiolates. 1, 8-naphthalenedithiol (NS2H2; N indicates naphthalene and S2 means two sulfur atoms as donor atoms) is used as ligand to form d10 metal dithiolate complexes. 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Chem. 1997, 36, 2294. 35 [...]... photophysics, photochemistry and structure properties of d10 metal- dithiolates 1, 8-naphthalenedithiol (NS2H2; N indicates naphthalene and S2 means two sulfur atoms as donor atoms) is used as ligand to form d10 metal dithiolate complexes The ligand is chosen partly because of its rather unexplored coordination chemistry but more importantly, unlike many 1, 1 -and 1, 2-dithiolates, 1, 8-naphthalenedithiolate is... 90 71 8 Siddique, Z A.; Yamamoto, Y.; Ohno, T.; Nozaki, K Inorg Chem 2003, 42, 4266 9 Huang, X C.; Zheng, S L; Zhang, J P.; Chen, X M Eur J Inorg Chem 2004, 10 24 10 Yam, V W W.; Lam C H; Fung, W K M.; Cheung, K K Inorg Chem 20 01, 40, 3435 11 Yam, V W W.; Cheng, E, C C.; Zhu, N Y Inorg Chem 20 01, 10 8, 10 29 12 Yam, V.W.W.; Cheng, E C C.; Cheng, K K Angew Chem 19 99 11 1, 19 3; Angew Chem Int Ed 19 99, 38, 19 7;... 19 99, 38, 19 7; 13 a) Vogler, A.; Kunkely, H Comments Inorg Chem 19 90, 9, 2 01. b) Kunkely, H.; Vogler, A Eur J Inorg Chem .19 98, 18 63 c) Kunkely, H.; Vogler, A Inorg Chim Acta 19 97, 264, 305 d) Benedix, R.; Vogler, A Inorg Chim Acta 19 93, 204, 18 9 e) Benedix, R.; Hennig, H.; Kunkely, H.; Vogler, A Chem Phys Lett 19 90, 17 5, 483 f) Stor, G J.; Stufkens, D J.; Oskam, A Inorg Chem 19 92, 31, 13 18 14 Acosta, A,... Fietz, H Angew Chem Int Ed 19 87, 26, 14 5 b) Henkel, G.; Krebs, B.; Betz, P.; Fietz, H.; Saatkamp, K.; Angew Chem.Int Ed 19 88, 27, 13 26 c)Birker P J M W.; Verschoor G C.; J Chem Soc., Chem Commun 19 81, 10 81, 322 19 92, 31, 2990 d) Bietrich, H Storck W Manecke G J Chem Soc., Chem 34 Commun 19 82, 10 36, 2990 e)Huang, Z.Y.; Lei, X J.; Hong, M C.; Liu, H Q Inorg Chem 19 92, 31 41 Henkel, G.; Krebs, B.; Betz,... D.T.; DiMartino, M J J Med Chem 19 72, 15 , 10 95 c) Hill, D.T.; Sutton, B M Cryst Struct Commun 19 80, 9, 679 d) Roy, P W.; Elder, R C.; and Teppeman, K Metal based Drugs, 19 94, 1, 5 21, Other articles in this issue of Metal Based Drugs also relate to this topic e) Sadler, P J in Metalcomplexes in Cancer Chemotherapy, Keppler K B., ed.; VCH, Weinheim, 19 93 3 a) Yasuda, H Yugagaku 19 90, 39, 798 b) Barone, G.;... Chem Rev 19 98, 17 1, 17 b)Yam, V.W.-W.; Lee, M K; Lai, T.-F J Chem Soc, Chem Commun 19 93, 15 71 c) Yam, V W W.; Cheng, E C C.; Zhou N Y New J Chem 2002, 26, 279.d) Yam, V W W.; Lam, C H.; Cheung, K K J Chem Soc., Chem Commun 20 01, 545 e) Yam, V W W.; Lo, K K W; Wang, C R; Cheung, K K J Phys Chem 19 97, 10 1, 4666 (f) Knotter, D M; Blasse, G.; van Vliet J P.M.; Van Koten, G Inorg Chem 19 92 31, 219 6 g) Knotter,... Hollander, F J.; Couconvains D J Am Chem Soc 19 77, 99 6268 28 Delepine, M Bull Soc Chim Fr 19 08, 3, 643 33 29 a) Coucouvanis, D Prog Inorg Chem 19 70, 11 , 233; 19 79, 26, 3 01 b) Burns, R P., McCullough, F P.; McAuliffe, C A Adv Inorg, Chem 19 80, 23, 211 c) Nieuwenhuizen, P J.; Ehlers, A.W.; Haasnoot, J G.; Janse, S R.; Reedijk, J.; Baerends, E J J Am Chem Soc 19 99, 12 1, 16 3 d)Pike, R D.; Cui, H.; Kershaw R.;... [(Ph3P)4Au4(í- SC6H4CH3)2](PF6)2 and [(dppe)2Au4(í-SC6H4CH3)2](PF6)2 separately (Figure 1. 11) The first tetranuclear cluster consisted two monocationic Au2(PPh3)2(í-SC6H4CH3)+ units via Au-Au interaction The latter Au4S2 core adopted a chair configuration with a gold single bond between Au (1) -Au(2) 2.9 61( 1) Å and a sulfur-bridged nonbonded Au-Au interaction of 3.844 Å 11 Figure 1. 11 2+ Ph Ph Ph P Au Ph Ph... emission range 495- 515 nm increased with more electron donating sulfur ligands Au complexes also exhibited low energy emission at ca 600 nm, attributed to a ligand-to -metal charge transfer (thiolate→Au(I)) origin Similar red shifts in emission energies were formed the basis for assignment of LMCT emission Figure 1. 12 R' N Ph2P PPh2 Au S Ph Au S R=F, R'=C6H 11 R=Cl, R'=C6H 11 R=Me, R'=C6H 11 R=Me, R'=Ph R=Me,... which indicated weak metal metal interactions compared to the sum of van der Waals radii for silver (3.4 Å) These complexes were found to exhibit luminescence at 77 K and the orange-red emission at 566 nm and 578 nm were tentatively attributed to originate from excited states of a mixture of metal- centred (MC) and metal metal bond-to-ligand charge-transfer (MMLT) character 13 Figure 1. 13 2+ Ph2 P Ph2 P . Cu Cu S S R R Cu Ph 2 P PPh 2 PPh 2 Ph 2 P Ph 2 P Ph 2 P R=C 6 H 4 -Cl-4 R=C 6 H 4 -CH 3 -4 R=C 6 H 4 -OCH 3 -4 R=C 6 H 3 -(OCH 3 ) 2 -3,4 R=benzo -15 -crown-5 R = t B u + (BF 4 - ) F i g u r e 1 . 1 4 1. 3 Structures of Polynuclear Au(I), Ag(I) and Cu(I) ditholate Complexes The chemistry of metal complexes contain 1, 1-dithiolate ligands. Ph Ph Ph S P Ph Ph Ph P Ph PhPh S Au Au Au Au Ph 2 P PH 2 S PPh 2 P P h 2 Ph 2 P F i g u r e 1 . 1 1 2+ 2+ At the same time a series of neutral, dinuclear gold(I) complexes, 21 (Figure 1. 12) containing phosphorous and sulfur ligands have been studied by. 1 Chapter 1 Structural and Spectroscopic Properties of d 10 Metal Thiolates 2 1. 1 Introduction Metal- thiolate complexes have been known since