Furan- and selenophene-2-carboxylato derivatives of dimolybdenum and ditungsten (M≡M): A comparison of their chemical and photophysical properties

Brown-Xu S.E.; Chisholm M.H.; Gallucci J.C.; Ghosh Y.; Gustafson T.L.; Reed C.R.

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Furan- and selenophene-2-carboxylato derivatives of dimolybdenum and ditungsten (M≡M): A comparison of their chemical and photophysical properties

机译：二钼和钨（M≡M）的呋喃-和硒基-2-羧基芳烃衍生物：化学和光物理性质的比较

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From the reactions between M _2(T iPB) _4, where T iPB = 2,4,6-triisopropylbenzoate and two equivalents each of 2-furan carboxylic acid, FuCO _2H, and 2-selenophene carboxylic acid, SpCO _2H in toluene, the new compounds trans-M _2(T iPB) _2(O _2CFu) _2 (1a M = Mo, 2a M = W) and trans-M _2(T iPB) _2(O _2CSp) _2 (1b M = Mo, 2b M = W) were formed. These new compounds have been characterized by ~1H NMR, steady-state UV-Vis-NIR absorption and emission spectroscopy, cyclic and differential pulse voltammetry, and fs and ns transient absorption spectroscopy. The compound Mo _2(T ~iPB) _2(O _2CSp) _2 (1b) has been characterized by single crystal X-ray crystallography. These data are compared with those previously reported for related 2-thiophene carboxylate derivatives: M _2(T ~iPB) _2(O _2CTh) _2. The physico-chemical data correlate well with electronic structure calculations performed on model compounds. All compounds have detectible S _1 photoexcited states with lifetimes that vary from ～5 ps to < 1 ps. The molybdenum compounds have T _1 states with microsecond lifetimes that are assigned as MMδδ* whereas the T _1 states for tungsten are ~3MLCT with lifetimes on the order of nanoseconds. In all cases, shorter lifetimes were seen in complexes containing heavier atoms.

机译：从M _2（T iPB）_4之间的反应（其中T iPB = 2,4,6-三异丙基苯甲酸酯）和两个当量的2-呋喃羧酸FuCO _2H和2-硒代羧酸SpCO _2H在甲苯中的反应，新化合物trans-M _2（T iPB）_2（O _2CFu）_2（1a M = Mo，2a M = W）和trans-M _2（T iPB）_2（O _2CSp）_2（1b M = Mo，2b M = W）形成。这些新化合物的特征在于〜1H NMR，稳态UV-Vis-NIR吸收和发射光谱，循环和差分脉冲伏安法以及fs和ns瞬态吸收光谱。化合物Mo _2（T〜iPB）_2（O _2CSp）_2（1b）已通过单晶X射线晶体学表征。将这些数据与先前报道的相关2-噻吩羧酸酯衍生物M _2（T〜iPB）_2（O _2CTh）_2进行比较。物理化学数据与对模型化合物进行的电子结构计算非常相关。所有化合物均具有可检测的S _1光激发态，其寿命从〜5 ps到<1 ps不等。钼化合物的T _1状态的微秒寿命被指定为MMδδ*，而钨的T _1状态的〜3MLCT寿命为纳秒量级。在所有情况下，在含有较重原子的配合物中观察到较短的寿命。

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《Dalton transactions: An international journal of inorganic chemistry》 |2012年第8期|共7页
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Brown-Xu S.E.; Chisholm M.H.; Gallucci J.C.; Ghosh Y.; Gustafson T.L.; Reed C.R.;
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机译：二钼和钨（M≡M）的呋喃-和硒基-2-羧基芳烃衍生物：化学和光物理性质的比较
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机译：钨 - 钨三重键。 7.在Hexakis（二甲基氨基）Ditungsten和-Dolyolybdenum化合物中用氯基取代二甲基酰胺;二氯四（二甲基氨基）二硫化物和二钼的制备，性质和结构。

Furan- and selenophene-2-carboxylato derivatives of dimolybdenum and ditungsten (M≡M): A comparison of their chemical and photophysical properties

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