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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Phosphorescent heterobimetallic complexes involving platinum(IV) and rhenium(VII) centers connected by an unsupported mu-oxido bridge
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Phosphorescent heterobimetallic complexes involving platinum(IV) and rhenium(VII) centers connected by an unsupported mu-oxido bridge

机译：磷光杂化物络合物涉及铂（IV）和铼（VII）中心由无支撑的Mu-Oxido桥连接的铂（VII）中心

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摘要

Heterobimetallic compounds [(C<^>N)LMe2Pt(mu-O)ReO3] (C<^>N = ppy, L = PPh3, 2a; C<^>N = ppy, L = PMePh2, 2b; C<^>N = bhq, L = PPh3, 2c; C<^>N = bhq, L = PMePh2, 2d) containing a discrete unsupported Pt(IV)-O-Re(VII) bridge have been synthesized through a targeted synthesis route. The compounds have been prepared by a single-pot synthesis in which the Pt(IV) precursor [PtMe2I(C<^>N)L] complexes are allowed to react easily with AgReO4 in which the iodide ligand of the starting Pt(IV) complex is replaced by an ReO4- anion. In these Pt-O-Re complexes, the Pt(IV) centers have an octahedral geometry, completed by a cyclometalated bidentate ligand (C<^>N), two methyl groups and a phosphine ligand, while the Re(VII) centers have a tetrahedral geometry. Elemental analysis, single crystal X-ray diffraction analysis and multinuclear NMR spectroscopy are used to establish their identities. The new complexes exhibit phosphorescence emission in the solid and solution states at 298 and 77 K, which is an uncommon property of platinum complexes with an oxidation state of +4. According to DFT calculations, we found that this emission behavior in the new complexes originates from ligand centered (LC)-L-3 (C<^>N) character with a slight amount of metal to ligand charge transfer ((MLCT)-M-3). The solid-state emission data of the corresponding cycloplatinated(IV) precursor complexes [PtMe2I(C<^>N)L], 1a-1d, pointed out that the replacement of I- by an ReO4- anion helps enhancing the emission efficiency besides shifting the emission wavelengths.
机译：异质金属化合物[（C <^> n）LME2PT（MU-O）REO3]（C n = PPY，L = PMEPH2,2B; C <^ > N = BHQ，L = PPH3，2C; C <^> N = BHQ，L = PMEPH2，2D）通过目标合成途径合成了含有离散的非支持的PT（IV）-O-RE（VII）桥的桥。该化合物已通过单罐合成制备，其中Pt（IV）前体[PTME2I（C + N）L]复合物容易用宜偶Pt（IV）的碘化物配体而对其进行反应复杂是由reo4-阴离子取代的。在这些PT-O-RE复合物中，PT（IV）中心具有八面体几何形状，由环级二齿配体（C + N），两个甲基和膦配体完成，而RE（VII）中心具有四面体几何形状。元素分析，单晶X射线衍射分析和多核NMR光谱用于建立其身份。新复合物在298和77k处表现出固体和溶液状态的磷光发射，这是铂复合物的罕见性，氧化态为+4。根据DFT计算，我们发现新复合物中的这种排放行为来自具有少量金属的配体中心（LC）-L-3（C <^> N）字符与配体电荷转移（（MLCT）-M -3）。相应的环塑酸化（IV）前体复合物的固态发射数据[PTME2I（C <^> N）L]，1A-1D指出，通过REO4-ANION的更换有助于提高排放效率移位发射波长。

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