Probing Framework-Restricted Metal Axial Ligation and Spin State Patterns in a Post-Synthetically Reduced Iron-Porphyrin-Based Metal-Organic Framework

被引:28
作者
Kucheryavy, Pavel [1 ]
Lahanas, Nicole [1 ]
Velasco, Ever [1 ]
Sun, Cheng-Jun [2 ]
Lockard, Jenny V. [1 ]
机构
[1] Rutgers State Univ, Dept Chem, Newark, NJ 07102 USA
[2] Argonne Natl Lab, Xray Sci Div, 9700 S Cass Ave, Argonne, IL 60439 USA
基金
美国国家科学基金会;
关键词
X-RAY-ABSORPTION; ELECTRONIC-STRUCTURE; EMISSION-SPECTROSCOPY; RESONANCE RAMAN; SPECTRA; COMPLEXES; TRANSITION; BETA; EDGE; STEREOCHEMISTRY;
D O I
10.1021/acs.jpclett.6b00302
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
An iron-porphyrin-based metal organic framework PCN-222(Fe) is investigated upon postsynthetic reduction with piperidine. Fe K-edge X-ray absorption and K beta mainline emission spectroscopy measurements reveal the local coordination geometry, oxidation, and spin state changes experienced by the Fe sites upon reaction with this axially coordinating reducing agent. Analysis and fitting of these data confirm the binding pattern predicted by a space-filling model of the structurally constrained pore environments. These results are further supported by UV vis diffuse reflectance, IR, and resonance Raman spectroscopy data.
引用
收藏
页码:1109 / 1115
页数:7
相关论文
共 46 条
[41]   SPIN-POLARIZED AND SITE-SELECTIVE X-RAY-ABSORPTION - DEMONSTRATION WITH FE PORPHYRINS AND K-BETA DETECTION [J].
WANG, X ;
RANDALL, CR ;
PENG, G ;
CRAMER, SP .
CHEMICAL PHYSICS LETTERS, 1995, 243 (5-6) :469-473
[42]   A multiplet analysis of Fe K-edge 1s->3d pre-edge features of iron complexes [J].
Westre, TE ;
Kennepohl, P ;
DeWitt, JG ;
Hedman, B ;
Hodgson, KO ;
Solomon, EI .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (27) :6297-6314
[43]   X-ray absorption spectroscopic investigation of the electronic structure differences in solution and crystalline oxyhemoglobin [J].
Wilson, Samuel A. ;
Green, Evan ;
Mathews, Irimpan I. ;
Benfatto, Maurizio ;
Hodgson, Keith O. ;
Hedman, Britt ;
Sarangi, Ritimukta .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2013, 110 (41) :16333-16338
[44]   Iron L-Edge X-ray Absorption Spectroscopy of Oxy-Picket Fence Porphyrin: Experimental Insight into Fe-O2 Bonding [J].
Wilson, Samuel A. ;
Kroll, Thomas ;
Decreau, Richard A. ;
Hocking, Rosalie K. ;
Lundberg, Marcus ;
Hedman, Britt ;
Hodgson, Keith O. ;
Solomon, Edward I. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (03) :1124-1136
[45]   Chemical Bond Characterization of a Mixed-Valence Tr-Cobalt Complex, Co3(μ-admtrz)4(μ-OH)2(CN)6•2H2O [J].
Wu, Lai-Chin ;
Weng, Tsu-Chien ;
Hsu, I-Jui ;
Liu, Yi-Hung ;
Lee, Gene-Hsiang ;
Jyh-Fu, Lee ;
Wang, Yu .
INORGANIC CHEMISTRY, 2013, 52 (19) :11023-11033
[46]   Spectroscopic study and electronic structure of prototypical iron porphyrins and their μ-oxo-dimer derivatives with different functional configurations [J].
Xu, Wei ;
Dziedzic-Kocurek, Katarzyna ;
Yu, Meijuan ;
Wu, Ziyu ;
Marcelli, Augusto .
RSC ADVANCES, 2014, 4 (87) :46399-46406