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Dinuclear (N∧C∧N) Pincer Pt(II) Complexes with Bridged Organometallic Linkers: Synthesis, Structures, Self-Aggregation, and Photophysical Properties
Organometallics ( IF 2.5 ) Pub Date : 2017-12-06 00:00:00 , DOI: 10.1021/acs.organomet.7b00680
Hugo Sesolis 1 , Carmen Ka-Man Chan 2 , Geoffrey Gontard 1 , Heidi Li-Ki Fu 2 , Vivian Wing-Wah Yam 2 , Hani Amouri 1
Affiliation  

A new family of cationic dinuclear cyclometalated Pt(II) complexes containing an organometallic assembling ligand has been reported. The general formulas for these compounds is as follow: [R-(NCN)Pt—L-L—Pt(NCN)-R][X]2, where L-L = [Cp*Ir-p-(η4-C6H4S2)], R = H, X = OTf (5); R= CF3–, X = OTf (6a), SbF6 (6b); L-L = [Cp*Ir-p-(η4-C6H4Se2)] R= CF3–, X = OTf (7a), SbF6 (7b). In these coordination assemblies two cyclometalated R-(NCN)Pt moieties are held by either η4-dithio-p-benzoquinone complex [Cp*Ir-p-(η4-C6H4S2)] (3) or η4-diseleno-p-benzoquinone complex [Cp*Ir-p-(η4-C6H4Se2)] (4). The molecular structures of the known complex [4-CF3-(NCN)PtCl] as well as two compounds of the above family [(NCN)Pt–Cp*Ir-p-(η4-C6H4S2)—Pt(NCN)][CF3SO3]2 (5) and [CF3-(NCN)Pt—Cp*Ir-p-(η4-C6H4S2)—Pt(NCN)-CF3][CF3SO3]2 (6a) were ascertained by single crystal X-ray diffraction study and confirmed the formation of the target molecules. The solid-state packing of 5 and 6a confirms the presence π–π and short Pt···Pt interactions among individual units providing 1D supramolecular chains. To our knowledge, these are the only known examples where two cyclometalated Pt(NCN) units are assembled by a bridging ligand (vide infra). All compounds show phosphorescence in the bluish-green region (486–521 nm) in the solution at room temperature and exhibit higher luminescence quantum yields relative to the analogous compounds containing a Pt(terpy) chromophore in thin film.

中文翻译:

双核(N Ç N)钳合铂(II)配合物的有机金属桥接连接体:合成,结构,自聚集,和光物理性质

已经报道了含有有机金属组装配体的阳离子双核环金属化的Pt(II)络合物的新家族。这些化合物的通式是如下:[R-(N Ç N)的Pt-LL-的Pt(N Ç N)-R] [X] 2,其中,LL =的[Cp * IR- p - (η 4 -C 6 H ^ 4 š 2)],R = H,X =光学传递函数(5); R = CF 3 –,X = OTf(6a),SbF 66b);LL =的[Cp * IR- p - (η 4 -C 6 H ^ 42)] R = CF 3 –,X = OTf(7a),SbF 67b)。在这些协调组件2环金属R-(N Ç N)的Pt部分通过任一η保持4 -dithio- p苯醌复合物的[Cp * IR- p - (η 4 -C 6 H ^ 4小号2)](3)或η 4 -diseleno- p苯醌复合物的[Cp * IR- p - (η 4 -C 6 H ^ 42)](4)。已知的复合物[4-CF的分子结构3 - (N ç 以及两个以上家庭的化合物[(N N)氯铂酸] Ç N)的Pt-的Cp * IR- p - (η 4 -C 6 ħ 4小号2)-Pt(N ç N)] [CF 3 SO 3 ] 25)和[CF 3 - (N ç N)的Pt-的Cp * IR- p - (η 4 -C 6 H 4 S 2)—铂(N Ç N)-CF 3 ] [CF 3 SO 3 ] 2图6a)通过单晶X射线衍射研究确定,并且确认了目标分子的形成。56a的固态堆积证实了提供一维超分子链的单个单元之间存在π-π和短Pt···Pt相互作用。据我们所知,这是已知的唯一的例子,其中两个环金属铂(N Ç N)个单元通过桥联配体组装(见下文)。相对于薄膜中包含Pt(terpy)发色团的类似化合物,所有化合物在室温下在溶液的蓝绿色区域(486-521 nm)中均显示磷光,并且显示出更高的发光量子产率。
更新日期:2017-12-06
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