Tuning the thermoelectric properties of metallo-porphyrins
Tuning the thermoelectric properties of metallo-porphyrins
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DOI：
10.1039/c5nr06966a
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发表时间：
2016-01-01
期刊：
影响因子：
6.7
通讯作者：
Lambert, Colin
中科院分区：
文献类型：
--
作者：
Al-Galiby, Qusiy H.;Sadeghi, Hatef;Lambert, Colin
我们研究了巯基连接到金电极上的金属卟啉的热电性质。通过改变Mn， Co, Ni, Cu， Fe和Zn族的过渡金属中心，我们能够调整相对于电极的费米能量的分子能级。得到的单分子室温热功率范围从Co和Cu中心几乎为零，到Ni和Zn中心分别为+80和+230 μ V K-1。相反，金属中心为Mn（II）或Fe（II）的热电功率为负，在-280 ~ -260 μ V K-1范围内。与反阴离子络合形成Fe（III）和Mn(III)，使它们的热功率的符号和大小分别变为+ 218和+ 95。预测Mn(II), Mn(III), Fe(III)， Zn和Fe（II）卟啉的室温功率因子分别为5.9 × 10(-5) W m(-1) K-2, 5.4 × 10(-4) W m(-1) K-2, 9.5 × 10(-4) W m(-1) K-2, 1.6 × 10(-4) W m(-1) K-2和2.3 × 10(-4) W m(-1) K-2，这使得这些材料成为分子尺度热电器件的有吸引力的材料。
We investigated the thermoelectric properties of metalloporphyrins connected by thiol anchor groups to gold electrodes. By varying the transition metal-centre over the family Mn, Co, Ni, Cu, Fe, and Zn we are able to tune the molecular energy levels relative to the Fermi energy of the electrodes. The resulting single-molecule room-temperature thermopowers range from almost zero for Co and Cu centres, to +80 mu V K-1 and +230 mu V K-1 for Ni and Zn respectively. In contrast, the thermopowers with Mn(II) or Fe(II) metal centres are negative and lie in the range -280 to -260 mu V K-1. Complexing these with a counter anion to form Fe(III) and Mn(III) changes both the sign and magnitude of their thermopowers to + 218 and + 95 respectively. The room-temperature power factors of Mn(II), Mn(III), Fe(III), Zn and Fe(II) porphyrins are predicted to be 5.9 x 10(-5) W m(-1) K-2, 5.4 x 10(-4) W m(-1) K-2, 9.5 x 10(-4) W m(-1) K-2, 1.6 x 10(-4) W m(-1) K-2 and 2.3 x 10(-4) W m(-1) K-2 respectively, which makes these attractive materials for molecular-scale thermoelectric devices.