TY - JOUR
T1 - Strong electronic influence of equatorial ligands on frontier orbitals in paddlewheel dichromium(ii,ii) complexes
AU - Huang, Po Jung
AU - Natori, Yoshiki
AU - Kitagawa, Yasutaka
AU - Sekine, Yoshihiro
AU - Kosaka, Wataru
AU - Miyasaka, Hitoshi
N1 - Funding Information:
This work was supported by a Grant-in-Aid for Scientific Research (Grant No. 16H02269 and 18K05055) from the Ministry of Education, Culture, Sports, Science, and Technology, Japan, and a Grand-in-Aid for Scientific Research on Innovative Areas (‘π-System Figuration’ Area 2601, No. 17H05137) from the Japan Society for the Promotion of Science, and the E-IMR project. P.-J. H. is thankful for the JSPS Research Fellowship for Young Scientists (No. 18J20896). Y. K. acknowledges Inter-University Cooperative Research Program of the Institute for Materials Research, Tohoku University (Proposal No. 17K0030 and 18K0048). Y. S. also acknowledges Shorai Foundation for Science and Technology.
Publisher Copyright:
© The Royal Society of Chemistry.
PY - 2019
Y1 - 2019
N2 - A series of substituted benzoate-bridged dichromium(ii,ii) complexes [Cr 2 (RCO 2 ) 4 (THF) 2 ] ([Cr 2 ]), where RCO 2 − is substituted benzoate, was synthesized and its structural and magnetic properties were investigated. The orbital energies, as well as magnetic coupling energies, were also investigated using computational approaches. The HOMO/LUMO energy levels of the complexes are strongly dependent on the acidity, i.e., pK a , of the corresponding benzoic acids (RCO 2 H), revealing a linear trend in the respective groups of non-ortho, mono-ortho, and bi-ortho substituted groups. The CrCr magnetic coupling constant (E S-T ) is little affected by pK a ; instead, the E S-T is associated with the HOMO/LUMO gap and strongly correlated with the CrCr distance.
AB - A series of substituted benzoate-bridged dichromium(ii,ii) complexes [Cr 2 (RCO 2 ) 4 (THF) 2 ] ([Cr 2 ]), where RCO 2 − is substituted benzoate, was synthesized and its structural and magnetic properties were investigated. The orbital energies, as well as magnetic coupling energies, were also investigated using computational approaches. The HOMO/LUMO energy levels of the complexes are strongly dependent on the acidity, i.e., pK a , of the corresponding benzoic acids (RCO 2 H), revealing a linear trend in the respective groups of non-ortho, mono-ortho, and bi-ortho substituted groups. The CrCr magnetic coupling constant (E S-T ) is little affected by pK a ; instead, the E S-T is associated with the HOMO/LUMO gap and strongly correlated with the CrCr distance.
UR - http://www.scopus.com/inward/record.url?scp=85060007801&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85060007801&partnerID=8YFLogxK
U2 - 10.1039/C8DT04347G
DO - 10.1039/C8DT04347G
M3 - Article
C2 - 30564819
AN - SCOPUS:85060007801
SN - 1477-9226
VL - 48
SP - 908
EP - 914
JO - Dalton Transactions
JF - Dalton Transactions
IS - 3
ER -