Luminescent di- and polynuclear organometallic gold(I)-metal (Au2, {Au2Ag}n and {Au2Cu}n) compounds containing bidentate phosphanes as active antimicrobial agents.
Luminescent di- and polynuclear organometallic gold(I)-metal (Au2, {Au2Ag}n and {Au2Cu}n) compounds containing bidentate phosphanes as active antimicrobial agents.
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DOI：
10.1002/chem.201103145
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发表时间：
2012-03-19
影响因子：
4.3
通讯作者：
Contel, Maria
中科院分区：
文献类型：
--
作者：
Frik, Malgorzata;Jimenez, Josefina;Gracia, Ismael;Falvello, Larry R.;Abi-Habib, Sarya;Suriel, Karina;Muth, Theodore R.;Contel, Maria
含均三甲苯配体的双核金（I）金属有机配合物[Au_2（mes）_2（μ-LL）]与桥联双齿膦的反应（LL = dppe：1，2-双（二苯基膦基）乙烷1a，和水溶性dppy：1,2-双（二-3-吡啶基膦基）乙烷（1b）与Ag+和Cu+的配位作用，形成了一类具有均三甲苯桥联配体的杂金属簇合物[Au_2 M（μ-mes）2（μ-LL）]A（M = Ag，A = ClO4−，L-L = dppe 2a，dppy 2b; M = Ag，A = SO3CF3−，L-L = dppe 3a，dppy 3b; M = Cu，A = PF6−，L-L = dppe 4a，dppy 4b）。用X射线单晶衍射法测定了[Au_2（mes）_2（μ-dppy）] 1b和[Au_2Ag（μ-mes）_2（μ-dppe）] SO_3CF_3_3a的晶体结构。3a在固态下不是环状三核Au_2Ag衍生物，而是由Ag（μ-mes）_2单元“连接”的{Au_2（μ-dppe）}片段形成开放的聚合物结构。2.7559（6）<$（Au-Ag）和2.9229（8）<$（Au-Au）的非常短的距离表明金银（亲金属）和亲金相互作用。系统研究了它们的发光性质，发现它们在固态、室温（RT）、77 K或冷冻DMSO溶液中都有明亮的发光，其寿命在微秒范围内，可能是由于[Au_2 M（μ-mes）_2（μ-LL）]~+单元的自聚集（M= Ag或Cu; LL= dppe或dppy）通过Au-Au和/或Au-M亲金属相互作用转化为延伸的链结构，如对于3a所观察到的。在固态下，Au_2 M与dppe（2a-4a）的异金属配合物的最大发射峰（从约100 nm）发生了位移，而dppe（2a-4a）的最大发射峰（从约100 nm）发生了位移。430至520-540 nm范围），而具有dppy的络合物（2b-4 b）显示出更适度的位移（1b的505至4 b的最大563 nm）。更重要的是，化合物[Au_2Ag（μ-mes）_2（μ-dppy）] ClO_4_2b在室温下在稀DMSO溶液中发光。为了比较的目的，还研究了以前报道的化合物[Au_2Cl_2（μ-LL）]（L-L dppy 5 b）。评价了1-5和阿加A（A= ClO 4-，OSO 2CF 3-）对革兰氏阳性和革兰氏阴性细菌和酵母的抗微生物活性。大多数测试的化合物显示出中等至高的抗菌活性，而具有dppe（2a-4a）的杂合Au 2 M衍生物具有更高的活性（MIC 10至1 μg/mL）。含银的化合物对革兰氏阴性菌的活性是母体双核化合物1a或银盐的10倍。Au_2Ag与dppy（2b，3b）的配合物对真菌也有较强的抑制作用。
The reaction of new dinuclear gold(I) organometallic complexes containing mesityl ligands and bridging bidentate phosphanes [Au2(mes)2(μ-LL)] (LL = dppe: 1,2-Bis(di-phenylphosphano)ethane 1a, and water-soluble dppy: 1,2-Bis(di-3-pyridylphosphano)ethane 1b) with Ag+ and Cu+ lead to the formation of a family of heterometallic clusters with mesityl bridging ligands of the general formula [Au2M(μ-mes)2(μ-LL)]A (M = Ag, A = ClO4−, L-L = dppe 2a, dppy 2b; M = Ag, A = SO3CF3−, L-L = dppe 3a, dppy 3b; M = Cu, A = PF6−, L-L = dppe 4a, dppy 4b). The new compounds were characterized by different spectroscopic techniques and mass spectrometry The crystal structures of [Au2(mes)2(μ-dppy)] 1b and [Au2Ag(μ-mes)2(μ-dppe)]SO3CF3 3a were determined by a single-crystal X-ray diffraction study. 3a in solid state is not a cyclic trinuclear Au2Ag derivative but it gives an open polymeric structure instead, with the {Au2(μ-dppe)} fragments “linked” by Ag(μ-mes)2 units. The very short distances of 2.7559(6) Å (Au-Ag) and 2.9229(8) Å (Au-Au) are indicative of gold-silver (metallophillic) and aurophilic interactions. A systematic study of their luminescence properties revealed that all compounds are brightly luminescent in solid state, at room temperature (RT) and at 77 K, or in frozen DMSO solutions with lifetimes in the microsecond range and probably due to the self-aggregation of [Au2M(μ-mes)2(μ-LL)]+ units (M= Ag or Cu; LL= dppe or dppy) into an extended chain structure, through Au-Au and/or Au-M metallophylic interactions, as that observed for 3a. In solid state the heterometallic Au2M complexes with dppe (2a–4a) show a shift of emission maxima (from ca. 430 to the range of 520–540 nm) as compared to the parent dinuclear organometallic product 1a while the complexes with dppy (2b–4b) display a more moderate shift (505 for 1b to a max of 563 nm for 4b). More importantly, compound [Au2Ag(μ-mes)2(μ-dppy)]ClO4 2b resulted luminescent in diluted DMSO solution at room temperature. Previously reported compound [Au2Cl2(μ-LL)] (L-L dppy 5b) was also studied for comparative purposes. The antimicrobial activity of 1–5 and AgA (A= ClO4−, OSO2CF3−) against Gram-positive and Gram-negative bacteria and yeast was evaluated. Most tested compounds displayed moderate to high antibacterial activity while heteronuclear Au2M derivatives with dppe (2a–4a) were the more active (MIC 10 to 1 μg/mL). Compounds containing silver were ten times more active to Gram-negative bacteria than the parent dinuclear compound 1a or silver salts. Au2Ag compounds with dppy (2b, 3b) were also potent against fungi.
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影响因子：
4
作者：
Bardají, M;Jones, PG;Villaverde, N
通讯作者：
Villaverde, N
影响因子：
20.6
作者：
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影响因子：
2.3
作者：
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作者：
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通讯作者：
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影响因子：
20.6
作者：
Barnard, Peter J.;Berners-Price, Susan J.
通讯作者：
Berners-Price, Susan J.