Influence of Sequential Solvation on Metal-to-Ligand Charge Transfer in Bis(2,2',2'-terpyridyl)iron(II) Clustered with Dimethyl Sulfoxide

Thomas G. Spence; Brett T. Trotter; Lynmarie A. Posey

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Influence of Sequential Solvation on Metal-to-Ligand Charge Transfer in Bis(2,2',2'-terpyridyl)iron(II) Clustered with Dimethyl Sulfoxide

机译：顺序溶剂化对二甲基亚砜成簇的双（2,2'，2“-吡啶基）铁（II）中金属到配体电荷转移的影响

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The first direct measurements of the contribution of individual solvent molecules to solvent reorganization associated with photoinitiated charge transfer in coordination complex are reported for gas-phase clusters of bis(2,2',2"-terpyridyl)iron(II), [Fe(terpy)_2]~(2+), with dimethyl sulfoxide (DMSO) prepared by electrospray ionization. Excitation of [Fe(terpy)_2·(DMSO)_n]~(2+) clusters at wavelengths corresponding to the metal-to-ligand charge-transfer (MLCT) absorption characteristic of Fe(II)-polypyridine complexes in solution triggers evaporation of solvent molecules, permitting the application of laser photofragmentation mass spectrometry to monitor MLCT absorption. The energy of the optical transition corresponding to MLCT E_(op) is reported for [Fe(terpy)_2·(DMSO)_n]~(2+) clusters (n = 1-11), and the cluster-size dependence of E_(op) is examined following Jortner's cluster-size-equation approach (Jortner, J. Z. Phys. D 1992, 24, 247). The first 11 DMSO molecules contribute 54-63% of the bulk solvent reorganization energy, based on estimates that E_(op) for the gas-phase [Fe(terpy)_2]~(2+) complex falls between 1.860 * 10~4 and 1.876 * 10~4 cm~(-1).

机译：据报道，双（2,2'，2“-吡啶基）铁（II），[Fe（）的气相簇中，单个溶剂分子对与配位络合物中光引发的电荷转移相关的溶剂重组的贡献的首次直接测量。 [Terpy）_2]〜（2+），用电喷雾电离制备的二甲基亚砜（DMSO）激发[Fe（terpy）_2·（DMSO）_n]〜（2+）团簇，其波长对应于金属对金属Fe（II）-聚吡啶配合物在溶液中的配体电荷转移（MLCT）吸收特性触发溶剂分子的蒸发，从而允许使用激光碎裂质谱法监测MLCT的吸收。与MLCT E_（op ）报告了[Fe（terpy）_2·（DMSO）_n]〜（2+）簇（n = 1-11），并根据Jortner的簇大小方程检查了E_（op）的簇大小依赖性。（Jortner，JZ Phys。D 1992，24，247）。前11种DMSO分子贡献54-63基于气相[Fe（terpy）_2]〜（2+）络合物的E_（op）介于1.860 * 10〜4和1.876 * 10〜4 cm〜（ -1）。

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |1998年第40期|共8页
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Thomas G. Spence; Brett T. Trotter; Lynmarie A. Posey;
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中图分类物理化学（理论化学）、化学物理学;
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1. Influence of Sequential Solvation on Metal-to-Ligand Charge Transfer in Bis(2,2',2"-terpyridyl)iron(II) Clustered with Dimethyl Sulfoxide [J] . Thomas G. Spence, Brett T. Trotter, Lynmarie A. Posey The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 1998,第40期

机译：顺序溶剂化对二甲基亚砜成簇的双（2,2'，2“-吡啶基）铁（II）中金属到配体电荷转移的影响
2. Switching between ligand-to-ligand charge-transfer, intraligand charge-transfer, and metal-to-ligand charge-transfer excited states in platinum(II) terpyridyl acetylide complexes induced by pH change and metal ions [J] . Han X, Wu LZ, Si G, Chemistry: A European journal . 2007,第26期

机译：pH值变化和金属离子诱导的铂（II）吡啶基乙炔化物络合物在配体到配体的电荷转移，配体内的电荷转移和金属到配体的电荷转移激发态之间切换
3. Switching between ligand-to-ligand charge-transfer, intraligand charge-transfer, and metal-to-ligand charge-transfer excited states in platinum(II) terpyridyl acetylide complexes induced by pH change and metal ions [J] . Han X, Wu LZ, Si G, Chemistry: A European journal . 2007,第26期

机译：pH值变化和金属离子诱导的铂（II）吡啶基乙炔化物络合物在配体到配体的电荷转移，配体内的电荷转移和金属到配体的电荷转移激发态之间切换
4. Linkage-isomerization and charge-transfer in the formation of iron mixed valence complexes, (n-C_3H_7)_4NFe~(II)Fe~(III)(dto)_3 (dto = C_2O_2S_2) and (n-C_4H_9)_4NFe~(II)Fe~(III)(mto)_3 (mto = C_2O_3S) [C] . K Kagesawa, N Kida, Y Ono, International conference on applications of the mossbauer effect;ICAME 2009 . 2009

机译：（n-C_3H_7）_4N Fe〜（II）Fe〜（III）（dto）_3（dto = C_2O_2S_2）和（n-C_4H_9）_4N形成铁键化和电荷转移Fe〜（II）Fe〜（III）（mto）_3（mto = C_2O_3S）
5. Towards the use of Adaptive Feedback Control Pulse Shaping to Probe and Control Reactivity of the Metal-to-Ligand Charge Transfer Excited State in Ruthenium(II) Bis-Terpyridine Complexes. [D] . Hewitt, Joshua Thomas. 2013

机译：致力于使用自适应反馈控制脉冲整形来探测和控制钌（II）双-三联吡啶配合物中金属到配体电荷转移激发态的反应性。
6. Crystal structure of bis(bis{μ3-3-methyl-3-(4-nitro-2-oxidobenzylidene)aminopropane-13-diolato}trischlorido(dimethyl sulfoxide)iron(III)) dimethyl sulfoxide heptasolvate dihydrate [O] . Eduard Chygorin, Yuri Smal, Irina V. Omelchenko 2016

机译：双（双{μ3-3-甲基-3-（4-硝基-2-氧化苄叉基）氨基丙烷-13-二醇基}三氯代（二甲基亚砜）铁（III））二甲基亚砜的晶体结构二水七溶剂化物
7. Crystal structure of bis(bis{μ3-3-methyl-3-[(4-nitro-2-oxidobenzylidene)amino]propane-1,3-diolato}tris[chlorido(dimethyl sulfoxide)iron(III)]) dimethyl sulfoxide heptasolvate dihydrate [O] . Eduard Chygorin, Yuri Smal, Irina V. Omelchenko 2016

机译：双（双{μ3-3-甲基-3 - [（4-硝基-2-氧代亚苄基）氨基]丙烷-1,3-二乙酸}三[氯代（二甲基亚砜）铁（III）]二甲基亚砜的晶体结构heptasolvate二水合物
8. Solvent Dependence of Metal-to-Ligand Charge-Transfer Transitions. Evidence for Initial Electron Localization in MLCT Excited States of 2,2'-Bipyridine Complexes of Ru(II) And Os(II) [R] . Kober, E. M., Sullivan, B. P., Meyer, T. J. 1983

机译：金属与配体电荷转移跃迁的溶剂依赖性。 Ru（II）和Os（II）2,2'-联吡啶配合物mLCT激发态初始电子定位的证据

Influence of Sequential Solvation on Metal-to-Ligand Charge Transfer in Bis(2,2',2'-terpyridyl)iron(II) Clustered with Dimethyl Sulfoxide

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