Electrochemistry, chemical reactivity, and time-resolved infrared spectroscopy of donor-acceptor systems [(Q(x))Pt(pap(y))] (Q = substituted o-quinone or o-iminoquinone; pap = phenylazopyridine).
Electrochemistry, chemical reactivity, and time-resolved infrared spectroscopy of donor-acceptor systems [(Q(x))Pt(pap(y))] (Q = substituted o-quinone or o-iminoquinone; pap = phenylazopyridine).
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DOI：
10.1021/ic4024713
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发表时间：
2014-01-21
影响因子：
4.6
通讯作者：
Sarkar B
中科院分区：
文献类型：
--
作者：
Deibel N;Schweinfurth D;Hohloch S;Delor M;Sazanovich IV;Towrie M;Weinstein JA;Sarkar B
研究了具有强π键相互作用和近红外吸收的给体-受体配合物[（O，NQ 2-）Pt（pap 0）]（1; pap =苯基偶氮吡啶，O，NQ 0 = 4，6-二叔丁基-N-苯基-邻亚氨基苯醌）的氧化还原反应性、电化学和激发态性质.单电子氧化产物[（O，NQ·-）Pt（pap 0）]（BF 4）（[1] BF 4）被化学分离。单晶X射线衍射研究确定了[1]+中O，NQ的亚氨基半醌形式。1记录在PPh 3的存在下的循环伏安图的模拟阐明了机制，并提供相关的热力学和动力学参数的氧化还原诱导的反应与PPh 3。通过X射线晶体学、电化学和电子顺磁共振光谱分析，分离出了该反应的结晶稳定产物[（O，NQ·-）Pt（PPh 3）2]（PF 6）（[2] PF 6）。配合物1b的皮秒时间分辨红外光谱研究（1的位置异构体之一）及其类似物[（O，OQ 2-）Pt（pap 0）]（三、O，OQ = 3，5-二叔丁基-邻苯醌）提供了对激发态动力学的深入了解，并揭示了酰胺基酚盐络合物1b中最低激发态的性质主要是基于二亚胺配体的，而在3的情况下，它主要是配体间电荷转移态。对[1]n+的密度泛函理论计算提供了对各种氧化还原形式和振动模式分配的前线轨道性质的进一步了解。我们讨论了新建立的氧化还原诱导的反应1与电子供体的机制的细节，并提出了这个过程的机制。报道了铂（II）与非无辜配体的给体-受体配合物。这些配合物的电子结构，氧化还原诱导的反应性和激发态动力学已被研究的电化学，光谱和理论方法相结合。
The donor–acceptor complex [(O,NQ2–)Pt(pap0)] (1; pap = phenylazopyridine, O,NQ0 = 4,6-di-tert-butyl-N-phenyl-o-iminobenzoquinone), which displays strong π-bonding interactions and shows strong absorption in the near-IR region, has been investigated with respect to its redox-induced reactivity and electrochemical and excited-state properties. The one-electron-oxidized product [(O,NQ•–)Pt(pap0)](BF4) ([1]BF4) was chemically isolated. Single-crystal X-ray diffraction studies establish the iminosemiquinone form of O,NQ in [1]+. Simulation of the cyclic voltammograms of 1 recorded in the presence of PPh3 elucidates the mechanism and delivers relevant thermodynamic and kinetic parameters for the redox-induced reaction with PPh3. The thermodynamically stable product of this reaction, complex [(O,NQ•–) Pt(PPh3)2](PF6) ([2]PF6), was isolated and characterized by X-ray crystallography, electrochemistry, and electron paramagnetic resonance spectroscopy. Picosecond time-resolved infrared spectroscopic studies on complex 1b (one of the positional isomers of 1) and its analogue [(O,OQ2–)Pt(pap0)] (3; O,OQ = 3,5-di-tert-butyl-o-benzoquinone) provided insight into the excited-state dynamics and revealed that the nature of the lowest excited state in the amidophenolate complex 1b is primarily diimine-ligand-based, while it is predominantly an interligand charge-transfer state in the case of 3. Density functional theory calculations on [1]n+ provided further insight into the nature of the frontier orbitals of various redox forms and vibrational mode assignments. We discuss the mechanistic details of the newly established redox-induced reactivity of 1 with electron donors and propose a mechanism for this process. Donor−acceptor complexes of platinum(II) with noninnocent ligands are reported. The electronic structures, redox-induced reactivity, and excited-state dynamics in these complexes have been investigated by a combination of electrochemical, spectroscopic, and theoretical methods.
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