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Zero-Magnetic-Field Splitting in the Excited Triplet States of Octahedral Hexanuclear Molybdenum(II) Clusters: [{Mo6X8}(n-C3F7COO)6]2– (X = Cl, Br, or I)
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2017-09-13 00:00:00 , DOI: 10.1021/acs.jpca.7b06783 Soichiro Akagi , Eri Sakuda 1 , Akitaka Ito 2 , Noboru Kitamura
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2017-09-13 00:00:00 , DOI: 10.1021/acs.jpca.7b06783 Soichiro Akagi , Eri Sakuda 1 , Akitaka Ito 2 , Noboru Kitamura
Affiliation
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Temperature (T)-dependent emission from [{Mo6X8}(n-C3F7COO)6]2– (X = Cl (1), Br (2), and I (3)) in optically transparent polyethylene glycol dimethacrylate matrices were studied in 3 K < T < 300 K to elucidate the spectroscopic and photophysical properties of the clusters, in special reference to zero-magnetic-field splitting (zfs) in the lowest-energy excited triplet states (T1) of the clusters. The cluster complexes 1 and 2 showed the T-dependent emission characteristics similar to those of [{Mo6Cl8}Cl6]2–, while 3 exhibited emission properties different completely from those of 1 and 2. Such T-dependent emission characteristics of 1, 2, and 3 were explained successfully by the excited triplet state spin-sublevel (Φn, n = 1–4) model. The zfs energies between the lowest-energy (Φ1) and highest-energy (Φ4) spin sublevels, ΔE14, resulted by the first-order spin–orbit coupling, were evaluated to be 650, 720, and 1000 cm–1 for 1, 2, and 3, respectively. The emission spectra of 1, 2, and 3 in CH3CN at 298 K were reproduced very well by the ΔE14 values and the population percentages of Φn at 300 K. We also report that the ΔE14 values of the clusters correlate linearly with the fourth power of the atomic number (Z) of X: ΔE14 ∝ {Z(X)}4.
中文翻译：
八面体六核钼（II）团簇的激发三重态的零磁场分裂：[{Mo 6 X 8 }（n -C 3 F 7 COO）6 ] 2–（X = Cl，Br或I）
温度（Ť）从依赖性发射[{沫6 X 8 }（Ñ -C 3 ˚F 7 COO）6 ] 2- （X =氯（1），溴（2）和I（3））在光学上透明的在3 K < T <300 K中研究了聚乙二醇二甲基丙烯酸酯基质，以阐明团簇的光谱和光物理性质，特别是在最低能量激发三重态（T 1）下的零磁场分裂（zfs ）的集群。簇复合物1和2显示出T依赖的发射特性与[{Mo 6 Cl 8 } Cl 6 ] 2–相似，而3的发射特性与1和2完全不同。这样Ť的依赖性的发射特性1，2，和3是由激发三重态自旋分段（Φ成功地解释Ñ，Ñ = 1-4）模型。最低能量（Φ之间的ZFS能量1）和最高的能量（Φ 4）旋能级，Δ È 14，导致由第一级的自旋轨道耦合，评价为650，720，和千厘米-1为1，2，和3，分别。的发射光谱1，2，和3在CH 3 CN在298K下再现非常好由Δ Ë 14值和Φ的人口百分比Ñ在300K我们还报告说，Δ Ë 14个的簇的值与X的原子序数（Z）的四次方线性相关：ΔE 14 ∝ { Z（X）} 4。
更新日期：2017-09-14
中文翻译：
八面体六核钼（II）团簇的激发三重态的零磁场分裂：[{Mo 6 X 8 }（n -C 3 F 7 COO）6 ] 2–（X = Cl，Br或I）
温度（Ť）从依赖性发射[{沫6 X 8 }（Ñ -C 3 ˚F 7 COO）6 ] 2- （X =氯（1），溴（2）和I（3））在光学上透明的在3 K < T <300 K中研究了聚乙二醇二甲基丙烯酸酯基质，以阐明团簇的光谱和光物理性质，特别是在最低能量激发三重态（T 1）下的零磁场分裂（zfs ）的集群。簇复合物1和2显示出T依赖的发射特性与[{Mo 6 Cl 8 } Cl 6 ] 2–相似，而3的发射特性与1和2完全不同。这样Ť的依赖性的发射特性1，2，和3是由激发三重态自旋分段（Φ成功地解释Ñ，Ñ = 1-4）模型。最低能量（Φ之间的ZFS能量1）和最高的能量（Φ 4）旋能级，Δ È 14，导致由第一级的自旋轨道耦合，评价为650，720，和千厘米-1为1，2，和3，分别。的发射光谱1，2，和3在CH 3 CN在298K下再现非常好由Δ Ë 14值和Φ的人口百分比Ñ在300K我们还报告说，Δ Ë 14个的簇的值与X的原子序数（Z）的四次方线性相关：ΔE 14 ∝ { Z（X）} 4。
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