LUMINESCENCE STUDIES OF GOLD(I) THIOLATE COMPLEXES
LUMINESCENCE STUDIES OF GOLD(I) THIOLATE COMPLEXES
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DOI：
10.1021/ic00129a019
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发表时间：
1995-12-06
影响因子：
4.6
通讯作者：
STAPLES, RJ
中科院分区：
文献类型：
--
作者：
FORWARD, JM;BOHMANN, D;STAPLES, RJ
合成了一系列含膦和硫醇配体的单体金配合物。使用的两种膦是三苯基膦和1，3，5-三氮杂-7-磷杂金刚烷三基膦（TPA）。使用取代的苯硫酚配体，其中取代基在邻位、Meta或帕拉。合成的所有化合物在固态下在77 K下发光，其中激发被分配给从硫醇盐配体的硫到金中心的配体到金属电荷转移（LMCT）跃迁。大的斯托克斯位移和长寿命的测量意味着发射磷光。发射最大值的位置可以受到硫醇盐配体上的取代基和固态中相邻分子之间的金-金相互作用的存在的影响。这些化合物中有四种已进行了结构表征。化合物3在棒（No.2）上以三斜晶系空间群P（1）结晶，晶胞常数a = 8.641（2）埃，B = 11.423（2）埃，c = 12.118（2）埃，α = 103.36（3）度，β = 99.34（3）度，γ = 105.95（3）度，和Z = 2。对2861个反射和253个参数进行细化，得到R = 0.0275和R（w）= 0.0669。化合物4以正交晶系空间群P2（1）2（1）2（1）（No.18）结晶，晶胞常数a = 6.3100（10）埃，B = 12.127（3）埃，c 18.193（3）埃，Z = 4。对1231个反射和163个参数进行细化，得到R = 0.0292和R（w）= 0.0360。化合物5以单斜晶系空间群P2（1）/n（No.13）结晶，晶胞常数a = 12.252（3）埃，B = 17.002（6）埃，c = 22.845（4）埃，β = 91.25（2）度和Z = 12。对5534个反射和541个参数的细化产生R = 0.0698和R（w）= 0.0786。化合物10以单斜空间群C2/c结晶（No.15），晶胞常数a = 17.542（5）埃，B = 18.831（6）埃，c = 11.647（4）埃，β = 119.52（2）度，Z = 8，对2207个反射和181个参数进行细化，得到R = 0.0327和R（w）= 0.0441。
A series of monomeric gold(I) complexes containing phosphine and thiolate ligands have been synthesized. The two phosphines used were triphenylphosphine and the 1,3,5-triaza-7-phosphaadamantanetriylphosphine (TPA). Substituted benzenethiolate ligands were used with the substituent in either the ortho, meta or para position. All of the compounds synthesized luminesce at 77 K in the solid state, where the excitation is assigned to a ligand to metal charge transfer (LMCT) transition from the sulfur of the thiolate ligand to the gold center. The large Stokes shifts and long lifetimes measured imply that the emission is phosphorescence. The position of the emission maxima can be affected by both the substituents on the thiolate ligand and the presence of gold-gold interactions between neighboring molecules in the solid state. Four of these compounds have been structurally characterized. Compound 3 crystallizes in the triclinic space group P (l) over bar (No. 2) with cell constants a = 8.641(2) Angstrom, b = 11.423(2) Angstrom, c = 12.118(2) Angstrom, alpha = 103.36(3)degrees, beta = 99.34(3)degrees, gamma = 105.95(3)degrees, and Z = 2. Refinement of 2861 reflections and 253 parameters yields R = 0.0275 and R(w) = 0.0669. Compound 4 crystallizes in the orthorhombic space group P2(1)2(1)2(1) (No. 18) with cell constants a = 6.3100(10) Angstrom, b = 12.127(3) Angstrom, c 18.193(3) Angstrom, and Z = 4. Refinement of 1231 reflections and 163 parameters yields R = 0.0292 and R(w) = 0.0360. Compound 5 crystallizes in the monoclinic space group P2(1)/n (No. 13) with cell constants a = 12.252(3) Angstrom, b = 17.002(6) Angstrom, c = 22.845(4) Angstrom, beta = 91.25(2)degrees and Z = 12. Refinement of 5534 reflections and 541 parameters yields R = 0.0698 and R(w) = 0.0786. Compound 10 crystallizes in the monoclinic space group C2/c (No. 15) with cell constants a = 17.542(5) Angstrom, b = 18.831(6) Angstrom, c = 11.647(4) Angstrom, beta = 119.52(2)degrees, and Z = 8, Refinement of 2207 reflections and 181 parameters yields R = 0.0327 and R(w) = 0.0441.