TY - JOUR
T1 - [Pt(SCN)4]2–-Based Coordination Polymers and Supramolecular Squares
T2 - Intermolecular Pt···H–C Interactions Probed by Luminescence Spectroscopy at Variable Pressure
AU - Suffren, Yan
AU - Kobayashi, Masayuki
AU - Ovens, Jeffrey S.
AU - Rodrigue-Witchel, Alexandre
AU - Genre, Caroline
AU - Sakai, Ken
AU - Reber, Christian
AU - Leznoff, Daniel B.
N1 - Funding Information:
We thank Carolyn Ladd and Kamila Bladek for help with some of the spectroscopic measurements. Financial support from the Natural Sciences and Engineering Research Council of Canada (NSERC) (D. B. L., C. R.) is gratefully acknowledged. J. S. O. is grateful to the NSERC for a PGS-D doctoral scholarship and to Natural Resources Canada for an internship. The present work was also supported by the Ministry of Education, Culture, Sports, Science and Technology of Japan, by a Grant-in-Aid for the Global COE Program, “Science for Future Molecular Systems”, as well as a Grant-in-Aid for Scientific Research (A) (No. 17205008), a Grant-in-Aid for Scientific Research on Priority Areas (No. 16074216 of 434: “Chemistry of Coordination Space”), and a Grant-in-Aid for Specially Promoted Research (No. 18002016). M. K. acknowledges a Research Fellowships from the Japan Society for the Promotion of Science for Young Scientist. D. B. L. is grateful to the Japan Society for the Promotion of Science (JSPS) for a Long-term Invitation Fellowship.
Publisher Copyright:
© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2017/6/16
Y1 - 2017/6/16
N2 - The structures of four types of supramolecular systems containing [Pt(SCN)4]2– molecular units have been characterized. [Mn(bipy)2Pt(SCN)4]2·2MeOH (1) and [Zn(bipy)2Pt(SCN)4]2·2MeOH (2) show cis-thiocyanato ligands bridging the PtII and MnII or ZnII ions, leading to a molecular square motif. [Zn(bipy)2Pt(SCN)4]2 (3) presents chains where trans-thiocyanato ligands bridge the ZnII and PtII ions. For 1–3, free thiocyanato ligands are coordinated to the PtII centers to complete the square-planar coordination. [Pb(bipy)2Pt(SCN)4]2 (4) reveals a two-dimensional sheet structure where all SCN– ligands bridge the PbII and PtII ions. [Pb(terpy)Pt(SCN)4]2 (5) is similar to 3, with two bridging trans-SCN– ligands and two that are coordinated only to the PtII centers. For all compounds, d–d luminescence is observed with band maxima at approximately 14600 cm–1 (690 nm). Spectra show characteristic shifts with pressure, indicative of either intramolecular or intermolecular effects, depending on the sign of the shift. The pressure-dependent shifts for 1–5 show rich variations. A well-documented shift to higher energy due to metal–ligand bond compression is observed for 5 and can be used as a basis for a comparison. Compounds 1–4 show a shift of Emax to lower energy with pressures below 10 kbar. A change in sign for the shift of Emax occurs at 20, 12, and 10 kbar for 1, 2, and 3, respectively. For 4, only a shift to lower energy is observed. Competing intra- and intermolecular effects lead to these variations.
AB - The structures of four types of supramolecular systems containing [Pt(SCN)4]2– molecular units have been characterized. [Mn(bipy)2Pt(SCN)4]2·2MeOH (1) and [Zn(bipy)2Pt(SCN)4]2·2MeOH (2) show cis-thiocyanato ligands bridging the PtII and MnII or ZnII ions, leading to a molecular square motif. [Zn(bipy)2Pt(SCN)4]2 (3) presents chains where trans-thiocyanato ligands bridge the ZnII and PtII ions. For 1–3, free thiocyanato ligands are coordinated to the PtII centers to complete the square-planar coordination. [Pb(bipy)2Pt(SCN)4]2 (4) reveals a two-dimensional sheet structure where all SCN– ligands bridge the PbII and PtII ions. [Pb(terpy)Pt(SCN)4]2 (5) is similar to 3, with two bridging trans-SCN– ligands and two that are coordinated only to the PtII centers. For all compounds, d–d luminescence is observed with band maxima at approximately 14600 cm–1 (690 nm). Spectra show characteristic shifts with pressure, indicative of either intramolecular or intermolecular effects, depending on the sign of the shift. The pressure-dependent shifts for 1–5 show rich variations. A well-documented shift to higher energy due to metal–ligand bond compression is observed for 5 and can be used as a basis for a comparison. Compounds 1–4 show a shift of Emax to lower energy with pressures below 10 kbar. A change in sign for the shift of Emax occurs at 20, 12, and 10 kbar for 1, 2, and 3, respectively. For 4, only a shift to lower energy is observed. Competing intra- and intermolecular effects lead to these variations.
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U2 - 10.1002/ejic.201700149
DO - 10.1002/ejic.201700149
M3 - Article
AN - SCOPUS:85017182073
VL - 2017
SP - 2865
EP - 2875
JO - Berichte der deutschen chemischen Gesellschaft
JF - Berichte der deutschen chemischen Gesellschaft
SN - 0365-9496
IS - 22
ER -