Counter anion dependent gradual spin transition in a 1D cobalt(<scp>ii</scp>) coordination polymer

Roy, Subhasis; Choubey, Somnath; Bhar, Kishalay; Sikdar, Nivedita; Costa, José Sánchez; Mitra, Partha; Ghosh, Barindra Kumar

doi:10.1039/c5dt00056d

Cited by 21 publications

(17 citation statements)

References 18 publications

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“…The ICP-OES analysis indicated that the {M(hfac)2} CP site is 70% Co and 30% Zn. The structural refinement of this site, as a mixture of Co & Zn, gave values consistent with this analysis (the zinc occupancy at 100 K was 0.34(5), at 150 K: 0.15 (6) and at 200 K: 0.39(6), averaging to 30% Zn occupancy). Since the same crystal was used throughout the variable temperature structural analysis, the occupancy of the site was fixed as 30%…”

Section: X-ray Crystallographysupporting

confidence: 78%

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Synthesis and properties of cobalt(II) coordination polymers linked by 4′-(4-pyridyl)-2,2′:6′,2″-terpyridine

et al. 2018

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The cationic one-dimensional coordination polymers [{Co(pyterpy)2}{M(hfac)2}] 2+ (M = Co(II) or Zn(II); pyterpy = 4'-(4-pyridyl)-2,2':6',2''-terpyridine; hfac-= hexafluoroacetyloacetonate) feature alternating {Co(pyterpy)2} and {M(hfac)2} units linked through heteroditopic pyterpy ligands. Cocrystallization with [M(hfac)3]-(M = Co(II) or Zn(II)) counteranions has afforded the compounds: [{Co(pyterpy)2}{Co(hfac)2}][Co(hfac) 3 ] 2 (1) and [{Co(pyterpy)2}{Co0.7Zn0.3(hfac)2}][Zn(hfac) 3 ] 2 (2). Variable temperature crystallographic and magnetic studies indicate low spin cobalt(II) ions in the {Co(pyterpy)2} components of the coordination polymers up to room temperature; magnetic studies suggest the onset of a thermallyinduced spin crossover at these centers above room temperature.

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Section: X-ray Crystallographysupporting

confidence: 78%

“…In some cases, a structural phase transition accompanies the SCO. To date, SCO has been reported for only a handful of cobalt CPs [4][5][6][7][8]. One of these families of SCO CPs has the general formula [CoX2(pyterpy)] where X = Cl -, Bror NCSand pyterpy = 4'-(4-pyridyl)-2,2':6',2''-terpyridine [4,7,8].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and properties of cobalt(II) coordination polymers linked by 4′-(4-pyridyl)-2,2′:6′,2″-terpyridine

et al. 2018

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“…In particular, the perchlorate counterion undergoes reorientation that affects the anion- interactions with the dicyanamide bridge, which seem to play a significant role in the cooperative character of the SCO transition. The phenomenon was later confirmed by studies of a hexafluorophosphate salt of the same complex, which undergoes a gradual and nonhysteretic SCO transition [57]. The non-coordinating bulky hexafluorophosphate counterion does not take part in the intermolecular interactions around the cobalt center, the result being a much less well-defined SCO conversion.…”

Section: Spin Crossover In One Dimensional Cobalt Coordination Polymersmentioning

confidence: 87%

Switchable cobalt coordination polymers: Spin crossover and valence tautomerism

Drath

Boskovic

2018

Coordination Chemistry Reviews

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Switchable cobalt coordination polymers exhibit valence tautomeric or spin crossover transitions upon application of an external stimulus such as heating or cooling.-One-and two-dimensional switchable cobalt coordination polymers are reviewed.-New directions in the field oriented towards materials applications include incorporating switchable cobalt coordination polymers into nano-and microparticles and grafting the particles onto surfaces.

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“…However, a ligand based on terpyridine and its derivatives have been used intensively. ,− It is reported that the coordination environment around a cobalt(II) center having a CoN 6 surrounding with all six donating nitrogen atoms coming from two neutral tridentate ligands generates [Co(L-N 3 ) 2 ] 2+ SCO complexes. In addition, extremely rare reports have explored the SCO properties of cobalt(II) with ligand systems different from terpyridine. − …”

Section: Introductionmentioning

confidence: 99%

Reversible Spin-State Switching and Tuning of Nuclearity and Dimensionality via Nonlinear Pseudohalides in Cobalt(II) Complexes

et al. 2020

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The self-assembly of a macrocyclic tetradentate ligand, cobalt(II) tetrafluoroborate, and nonlinear pseudohalides (dicyanamide and tricyanomethanide) has led to two cobalt(II) N′-di-tert-butyl-2,11diaza[3,3](2,6)pyridinophane; dca − = dicyanamido; tcm − = tricyanomethanido). Both complexes were characterized by single-crystal X-ray diffraction, spectroscopic, magnetic, and electrochemical studies. Structural analyses revealed that 1 displays a one-dimensional (1D) coordination polymer containing [Co-(L)] 2+ repeating units bridged by μ 1,5 -dicyanamido groups in cis positions, while 2 represents a discreate dinuclear cobalt(II) molecule bridged by two μ 1,5 -tricyanomethanido groups in a cis conformation. Both complexes have a CoN 6 coordination environment around each cobalt center offered by the tetradentate ligand and cis coordinating bridging ligands. Complex 1 exhibits a high-spin (S = 3/2) state of cobalt(II) in the temperature range of 2−300 K with a weak ferromagnetic coupling between two dicyanamido-bridged cobalt(II) centers. Interestingly, complex 2 exhibits reversible spin-state switching associated with spin−spin coupling. Complexes 1 and 2 also exhibit interesting redox-stimuli-based reversible paramagnetic high-spin cobalt(II) to diamagnetic low-spin cobalt(III) conversion, offering an additional way to switch magnetic properties. A detailed theoretical calculation was consistent with the stated results.

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Counter anion dependent gradual spin transition in a 1D cobalt(ii) coordination polymer

Cited by 21 publications

References 18 publications

Synthesis and properties of cobalt(II) coordination polymers linked by 4′-(4-pyridyl)-2,2′:6′,2″-terpyridine

Synthesis and properties of cobalt(II) coordination polymers linked by 4′-(4-pyridyl)-2,2′:6′,2″-terpyridine

Switchable cobalt coordination polymers: Spin crossover and valence tautomerism

Reversible Spin-State Switching and Tuning of Nuclearity and Dimensionality via Nonlinear Pseudohalides in Cobalt(II) Complexes

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