Mixed-Metal Cu–Zn Thiocyanate Coordination Polymers with Melting Behavior, Glass Transition, and Tunable Electronic Properties

Wechwithayakhlung, Chayanit; Wannapaiboon, Suttipong; Na-Phattalung, Sutassana; Narabadeesuphakorn, Phisut; Tanjindaprateep, Similan; Waiprasoet, Saran; Imyen, Thidarat; Horike, Satoshi; Pattanasattayavong, Pichaya

doi:10.1021/acs.inorgchem.1c01813

Cited by 5 publications

(5 citation statements)

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“…[45,46]) and similar to previously reported data of CuSCN. [ 47,48 ] Interestingly, we observe that the pristine CuSCN sample exhibited a noticeably lower white line intensity (strong absorption peak after the edge, at 8997 eV in this case) than the CuSCN standard, indicating a slightly lower coordination number of the Cu atoms in the pristine sample. [ 49–51 ] As discussed below in the EXAFS analysis, the incomplete coordination around Cu + centers is restored at the optimal I 2 doping concentration of 0.5 mol.%.…”

Section: Resultsmentioning

confidence: 86%

Origin of Hole‐Trapping States in Solution‐Processed Copper(I) Thiocyanate and Defect‐Healing by I₂ Doping

Worakajit

Kidkhunthod

Thanasarnsurapong

et al. 2023

Adv Funct Materials

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Solution‐processed copper(I) thiocyanate (CuSCN) typically exhibits low crystallinity with short‐range order; the defects result in a high density of trap states that limit the device's performance. Despite the extensive electronic applications of CuSCN, its defect properties are not understood in detail. Through X‐ray absorption spectroscopy, pristine CuSCN prepared from the standard diethyl sulfide‐based recipe is found to contain under‐coordinated Cu atoms, pointing to the presence of SCN− vacancies. A defect passivation strategy is introduced by adding solid I2 to the processing solution. At small concentrations, the iodine is found to exist as I− which can substitute for the missing SCN− ligand, effectively healing the defective sites and restoring the coordination around Cu. Computational study results also verify this point. Applying I2‐doped CuSCN as a p‐channel in thin‐film transistors shows that the hole mobility increases by more than five times at the optimal doping concentration of 0.5 mol.%. Importantly, the on/off current ratio and the subthreshold characteristics also improve as the I2 doping method leads to the defect‐healing effect while avoiding the creation of detrimental impurity states. An analysis of the capacitance‐voltage characteristics corroborates that the trap state density is reduced upon I2 addition.

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Section: Resultsmentioning

confidence: 86%

Origin of Hole‐Trapping States in Solution‐Processed Copper(I) Thiocyanate and Defect‐Healing by I₂ Doping

Worakajit

Kidkhunthod

Thanasarnsurapong

et al. 2023

Adv Funct Materials

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“…In view of our ,, and other groups ,, interest in noncovalent bonding patterns of metal coordinated thiocyanates, in this study, we analyzed M···SCN–M′ contacts and classified them as linear and bent (Figure ). The results of our CSD search indicate that, in the overwhelming majority of the reported structures, ∠MSC of M···SCN–M′ short separations are spanning the range between 80 and 120° (Figure B).…”

Section: Discussionmentioning

confidence: 99%

Linear and Bent Noncovalent M···S═C═N–M′ Interactions: The Case of Palladium(II) and Platinum(II) Thiocyanate Species

Kashina

Kinzhalov

Tupikina

et al. 2023

Crystal Growth & Design

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Analysis of X-ray crystal structures of newly prepared thiocyanate PdII and PtII complexes revealed the bifurcated (M–N)···S contacts in which angles ∠M···SC are close to 180°. All M···SCN–M′ noncovalent interactionsidentified in this study and also those found on the Cambridge Structural Database searchwere systematized as linear (approximately 180°) and bent (∠M···SC 80–120°). Results of appropriate theoretical study indicate that, although the linear configuration of the PdII and PtII structures is primarily determined by crystal packing effects, the attractive M···S forces are far from negligible and the linear structures correspond to the energy minimum. Furthermore, the linear arrangement is mostly determined by orbital interactions, while the bent configuration by electrostatic forces. Molecular electrostatic potential (MEP) surfaces along with the quantum theory of “atoms-in-molecules” (QTAIM) and the noncovalent interaction plot index (NCIPlot) computational tools were used to characterize the bifurcated (M–N)···S interactions. The nature of the noncovalent M···SCN–M′ forces in the PdII and PtII structures was established by NBO analysis: in both cases, the predominant donor–acceptor orbital interactions include the charge transfer from lone pair orbitals located at the M atom to the σ*-orbital of the S–C bond of a thiocyanate ligand from a neighboring complex.

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“…84,91,92 Recent reports also suggest that solid solutions of Cu(I) and Zn(II) thiocyanates may also melt, though inhomogeneously. 93…”

Section: Alkali Metalsmentioning

confidence: 99%

Inorganic Metal Thiocyanates

Cliffe

2024

Preprint

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Metal thiocyanates are some of the earliest reported molecular framework materials and adopta diverse range of structures. This review describes the structures, properties and syntheses ofthe known binary and ternary thiocyanates. It provides a categorization of their diverse structures,and connects them to the structures of atomic inorganic materials. In addition to this description ofcharacterized binary and ternary thiocyanates, the review summarizes the state of knowledge forall other binary metal thiocyanates. The review concludes by highlighting opportunities for futurematerials development.

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Mixed-Metal Cu–Zn Thiocyanate Coordination Polymers with Melting Behavior, Glass Transition, and Tunable Electronic Properties

Cited by 5 publications

References 76 publications

Origin of Hole‐Trapping States in Solution‐Processed Copper(I) Thiocyanate and Defect‐Healing by I₂ Doping

Origin of Hole‐Trapping States in Solution‐Processed Copper(I) Thiocyanate and Defect‐Healing by I₂ Doping

Linear and Bent Noncovalent M···S═C═N–M′ Interactions: The Case of Palladium(II) and Platinum(II) Thiocyanate Species

Inorganic Metal Thiocyanates

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Mixed-Metal Cu–Zn Thiocyanate Coordination Polymers with Melting Behavior, Glass Transition, and Tunable Electronic Properties

Cited by 5 publications

References 76 publications

Origin of Hole‐Trapping States in Solution‐Processed Copper(I) Thiocyanate and Defect‐Healing by I2 Doping

Origin of Hole‐Trapping States in Solution‐Processed Copper(I) Thiocyanate and Defect‐Healing by I2 Doping

Linear and Bent Noncovalent M···S═C═N–M′ Interactions: The Case of Palladium(II) and Platinum(II) Thiocyanate Species

Inorganic Metal Thiocyanates

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Product

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Origin of Hole‐Trapping States in Solution‐Processed Copper(I) Thiocyanate and Defect‐Healing by I₂ Doping

Origin of Hole‐Trapping States in Solution‐Processed Copper(I) Thiocyanate and Defect‐Healing by I₂ Doping