Pt(II)[(2,2′-bpy)(NCO)2] (2,2′-bpy = 2,2′-bipyridyl): an X-ray structure, NMR and FT-IR determination of pseudohalide bonding

Coyer, M. J.; Herber, Rolfe H.; Cohen, Shmuel

doi:10.1016/s0020-1693(00)83196-5

Cited by 13 publications

(8 citation statements)

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“…It has previously been shown that the 13 C chemical shifts of S- and N-bound thiocyanate are lower and higher than the value for ionic thiocyanate (134.0 ppm), respectively. , The shifts in both of the above complexes conform to this rule but are significantly greater than those in [Au(SCN) 2 ] - (116.3 ppm) or [Hg(SCN) 4 ] 2- (124.8 ppm) and are higher than those observed for a range of other diamagnetic S-bound thiocyanate complexes, while still remaining less than that for ionic thiocyanate. It has been claimed that the 13 C chemical shift of O-bound cyanate lies in the range 104−119 ppm, while that of N-bound cyanate occurs in the range 114−132 ppm. , The value observed in the present work for Hg 2 (NCO) 2 significantly extends the upper limit of the N-bound range to 138 ppm. The values reported for a number of other N-bound cyanate complexes lie below the value for ionic cyanate (127.9 ppm), , and Hg 2 (NCO) 2 is an unusual case in which the shift lies above this value.…”

Section: Resultssupporting

confidence: 54%

“…It has been claimed that the 13 C chemical shift of O-bound cyanate lies in the range 104−119 ppm, while that of N-bound cyanate occurs in the range 114−132 ppm. , The value observed in the present work for Hg 2 (NCO) 2 significantly extends the upper limit of the N-bound range to 138 ppm. The values reported for a number of other N-bound cyanate complexes lie below the value for ionic cyanate (127.9 ppm), , and Hg 2 (NCO) 2 is an unusual case in which the shift lies above this value.…”

Section: Resultssupporting

confidence: 54%

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Solid-State ¹⁹⁹Hg MAS NMR and Vibrational Spectroscopic Studies of Dimercury(I) Compounds

1999

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The solid-state (199)Hg MAS NMR spectra of Hg(2)X(2) (X = Cl, SCN, NCO, CH(3)CO(2), CF(3)CO(2)) have been measured, and the infrared and Raman spectra of these compounds have been recorded and analyzed to further characterize them and to assist in the interpretation of the NMR data. Spinning-sideband analysis has been used to determine the (199)Hg shielding anisotropy and asymmetry parameters Deltasigma and eta from the solid-state (199)Hg MAS NMR spectra. In contrast to the case of the corresponding mercury(II) compounds, the shielding anisotropy is found to be relatively insensitive to the nature of the X group. This is consistent with the view that the electronic environment of the Hg atom in the mercury(I) compounds is dominated by the Hg-Hg bond. The changes in the (199)Hg shielding parameters from the mercury(II) to the corresponding mercury(I) compounds, as well as the changes in these parameters in the mercury(I) compounds with changes in X, can be interpreted in terms of variations in the local paramagnetic contribution to the shielding tensor.

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Section: Resultssupporting

confidence: 54%

Section: Resultssupporting

confidence: 54%

Solid-State ¹⁹⁹Hg MAS NMR and Vibrational Spectroscopic Studies of Dimercury(I) Compounds

1999

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“…Although there are many examples of such materials, we have found few structural reports of platinum(ID diimine compounds forming such chains [Osborn & Rogers, 1974;Che, He, Poon & Mak, 1989;Coyer, Herber & Cohen, 1990, 1991(see Marsh, 1994; Biedermann, Gliemann, Klement, Range & Zabel, 1990]. In all but one of these reported structures, successive platinum diimine molecules are rotated by 180 ° about the chain axis, so that eclipsing of the ligands is avoided and the Pt...Pt...Pt chain is slightly zigzag.…”

Section: Introductionmentioning

confidence: 99%

A revision of the structure of (bipyridyl-N,N')-dicyanoplatinum(II)

Connick¹,

Henling²,

Marsh³

1996

Acta Crystallogr Sect B

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In a previous X-ray crystallographic study of crystals of Pt(bpy)(CN) 2 (bpy = 2,2'-bipyridine) the planar molecules were reported to be exactly eclipsed, stacked directly on top of one another with a spacing of 3.33 A so as to form a linear Pt...Pt...Pt chain. A reinvestigation shows this structure to be incorrect. The presence of weak intermediate layer lines indicates that the repeat distance along the stacking direction is 6.66A rather than 3.33 A. Successive molecules within the stack are rotated by 180 ° and the resulting Pt-atom chain is slightly zigzag with a Pt...Pt...Pt angle of 168.6(1) °. The implications are discussed of the determination and refinement of an apparently satisfactory, although grossly wrong, structure that was based on an incorrect unit cell and an incorrect space group.

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“…Second, platinum(II) moieties in all six structures show an alternate arrangement of antiparallel and staggered packing patterns and stack the 1D “Pt wire” structure along the c axis (Figures and S3–S9). In contrast, only one kind of packing pattern (mainly antiparallel packing pattern) is usually adopted in the 1D “Pt wire” structure of small molecular platinum(II) complexes such as Pt(bpy)Cl 2 , Pt(bpm)Cl 2 · 1 / 2 nmp, Pt(bpy)(NCS) 2 , Pt(bpy)(NCO) 2 , Pt(bpy)(CN) 2 , Pt(bpm)(CN) 2 ·DMF, Pt(dmbpy)(NCO) 2 , Pt(phen)(CN) 2 , and Pt(bph)(CO) 2 . − It has been well-known that the staggered packing pattern of diimineplatinum(II) complexes can effectively reduce the effect of steric hindrance of substituents during molecular stacking and is helpful for the formation of intermolecular Pt–Pt interactions. , Therefore, an alternate arrangement of two packing patterns is more conducive for a molecule containing larger sterically hindered substituents to construct a stable 1D “Pt wire” stacking structure.…”

Section: Resultsmentioning

confidence: 99%

“…Second, in most cases, the combination of a 1D “Pt wire” structure and other strategies to further reduce the emission energy of a platinum(II) complex is mutually limited. As a result, the luminescence of most platinum(II) complexes with a 1D “Pt wire” structure is still in the visible region. − Therefore, the development of a new strategy to achieve high-efficiency long-wavelength NIR luminescence of a diimineplatinum(II) complex is very important and necessary.…”

Section: Introductionmentioning

confidence: 99%

Strategy for Achieving Long-Wavelength Near-Infrared Luminescence of Diimineplatinum(II) Complexes

Jiajia

et al. 2021

Inorg. Chem.

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Although many strategies have been used to help design effective near-infrared (NIR) luminescent materials, it is still a huge challenge to realize long-wavelength NIR luminescence of diimineplatinum(II) complexes in the solid state. Herein, we have successfully achieved long-wavelength NIR luminescence of a family of diimineplatinum(II) complexes based on a new strategy that combines a one-dimensional (1D) "Pt wire" structure with the electronic effect of the substituent. The structures of six solvated diimineplatinum(II) complexes based on 4,4-dichloro-2,2′-bipyridine or 4,4-dibromo-2,2′-bipyridine and 4-substituted phenylacetylene ligands have been determined, namely, and 6• 1 / 4 toluene. All of them crystallize in the monoclinic space group C2/c or C2/ m and stack in the 1D "Pt wire" structure. In the solid state, six complexes exhibited unusual long-wavelength metal−metal-to-ligand charge-transfer luminescence that peaked at 984, 1044, 972, 990, 1022, and 935 nm, respectively. Interestingly, 2• 1 / 2 THF has the shortest Pt•••Pt distance and the longest emission wavelength among the six complexes. As far as we know, the luminescence of 2• 1 / 2 THF at 1044 nm is the longest emission wavelength among known diimineplatinum(II) complexes. Systematic studies revealed that good molecular planarity, suitable substituent position, weak hydrogen-bond-forming ability of the substituents, appropriate molecular bending, and weakening of the interaction between solvated molecules and platinum molecules are conducive to the construction of a 1D "Pt wire" structure of the diimineplatinum(II) complex. Furthermore, the emission energy of the complex is mainly determined by the strength of the Pt−Pt interaction and electronic effect of the substituent.

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Pt(II)[(2,2′-bpy)(NCO)2] (2,2′-bpy = 2,2′-bipyridyl): an X-ray structure, NMR and FT-IR determination of pseudohalide bonding

Cited by 13 publications

References 49 publications

Solid-State ¹⁹⁹Hg MAS NMR and Vibrational Spectroscopic Studies of Dimercury(I) Compounds

Solid-State ¹⁹⁹Hg MAS NMR and Vibrational Spectroscopic Studies of Dimercury(I) Compounds

A revision of the structure of (bipyridyl-N,N')-dicyanoplatinum(II)

Strategy for Achieving Long-Wavelength Near-Infrared Luminescence of Diimineplatinum(II) Complexes

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Pt(II)[(2,2′-bpy)(NCO)2] (2,2′-bpy = 2,2′-bipyridyl): an X-ray structure, NMR and FT-IR determination of pseudohalide bonding

Cited by 13 publications

References 49 publications

Solid-State 199Hg MAS NMR and Vibrational Spectroscopic Studies of Dimercury(I) Compounds

Solid-State 199Hg MAS NMR and Vibrational Spectroscopic Studies of Dimercury(I) Compounds

A revision of the structure of (bipyridyl-N,N')-dicyanoplatinum(II)

Strategy for Achieving Long-Wavelength Near-Infrared Luminescence of Diimineplatinum(II) Complexes

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Product

Resources

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Solid-State ¹⁹⁹Hg MAS NMR and Vibrational Spectroscopic Studies of Dimercury(I) Compounds

Solid-State ¹⁹⁹Hg MAS NMR and Vibrational Spectroscopic Studies of Dimercury(I) Compounds