PMID- 27058604
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20170710
LR  - 20210927
IS  - 1520-510X (Electronic)
IS  - 0020-1669 (Linking)
VI  - 55
IP  - 9
DP  - 2016 May 2
TI  - Valence Tautomerism in One-Dimensional Coordination Polymers.
PG  - 4141-51
LID - 10.1021/acs.inorgchem.5b02812 [doi]
AB  - The combination of the divergent bis-pyridyl linking ligands 
      1,2-bis(4-pyridyl)ethane (1,2-bpe), 4,4'-trans-azopyridine (azpy), and 
      1,3-bis(4-pyridyl)propane (1,3-bpp) with cobalt and 3,5-di-tert-butyldioxolene 
      (3,5-dbdiox) ligands has afforded the complexes [Co(3,5-dbdiox)2(1,2-bpe)]infinity (1), 
      [Co(3,5-dbdiox)2(azpy)]infinity (2), [trans-Co(3,5-dbdiox)2(1,3-bpp)]infinity (3a), and 
      [cis-Co(3,5-dbdiox)2(1,3-bpp)]infinity (3b). All species are 1D coordination polymers 
      that crystallize as solvated forms; the geometric isomers 3a,b cocrystallize. 
      Complexes 1, 2, and 3a exhibit around the Co centers a trans disposition of the 
      N-donor atoms from the pyridyl linkers, while an unusual cis disposition is 
      evident in 3b. Single-crystal X-ray structural analysis at 100 or 130 K of 
      solvated forms of these complexes indicates that all complexes possess the 
      Co(III)(3,5-dbcat)(3,5-dbsq) (3,5-dbcat = 3,5-di-tert-butylcatecholate; 
      3,5-dbsq = 3,5-di-tert-butylsemiquinonate) charge distribution at the temperature 
      of data collection. Variable-temperature magnetic susceptibility studies reveal 
      that 1, 1.1.5MeCN.2H2O, 2.2EtOH, and 3.MeCN.H2O (3 = 3a.3b) all exhibit thermally 
      induced valence tautomeric (VT) transitions above 200 K. Multiple heating and 
      cooling cycles indicate that in some cases the behavior is strongly dependent on 
      desolvation processes. Most notably, further desolvation of 1.1.5MeCN.2H2O above 
      340 K affords chimT values that suggest unusual ferromagnetic coupling in the 
      hs-Co(II)(3,5-dbsq)2 valence tautomer. Compound 3.MeCN.H2O exhibits a two-step 
      VT transition that may be ascribed to the presence of the cis and trans geometric 
      isomers. Compounds 1, 1.1.5MeCN.2H2O, 2.2EtOH, and 3.MeCN.H2O all also exhibit a 
      single photoinduced VT transition, comparable to those generally observed for 
      nonpolymeric cobalt-dioxolene complexes.
FAU - Drath, Olga
AU  - Drath O
AD  - School of Chemistry, University of Melbourne , Victoria 3010, Australia.
FAU - Gable, Robert W
AU  - Gable RW
AD  - School of Chemistry, University of Melbourne , Victoria 3010, Australia.
FAU - Moubaraki, Boujemaa
AU  - Moubaraki B
AD  - School of Chemistry, Monash University , Clayton 3800, Australia.
FAU - Murray, Keith S
AU  - Murray KS
AD  - School of Chemistry, Monash University , Clayton 3800, Australia.
FAU - Poneti, Giordano
AU  - Poneti G
AD  - UdR INSTM and Department of Chemistry "U. Schiff'', University of Florence , 50019 
      Sesto Fiorentino (FI), Italy.
FAU - Sorace, Lorenzo
AU  - Sorace L
AD  - UdR INSTM and Department of Chemistry "U. Schiff'', University of Florence , 50019 
      Sesto Fiorentino (FI), Italy.
FAU - Boskovic, Colette
AU  - Boskovic C
AD  - School of Chemistry, University of Melbourne , Victoria 3010, Australia.
LA  - eng
GR  - 267746/ERC_/European Research Council/International
PT  - Journal Article
DEP - 20160408
PL  - United States
TA  - Inorg Chem
JT  - Inorganic chemistry
JID - 0366543
EDAT- 2016/04/09 06:00
MHDA- 2016/04/09 06:01
CRDT- 2016/04/09 06:00
PHST- 2016/04/09 06:00 [entrez]
PHST- 2016/04/09 06:00 [pubmed]
PHST- 2016/04/09 06:01 [medline]
AID - 10.1021/acs.inorgchem.5b02812 [doi]
PST - ppublish
SO  - Inorg Chem. 2016 May 2;55(9):4141-51. doi: 10.1021/acs.inorgchem.5b02812. Epub 
      2016 Apr 8.