The theoretical data for the half‐lantern complexes [{Pt(trueCN^
)(μ‐trueSN^
)}2] [1–3; trueCN^
is cyclometalated 2‐Ph‐benzothiazole; trueSN^
is 2‐SH‐pyridine (1), 2‐SH‐benzoxazole (2), 2‐SH‐tetrafluorobenzothiazole (3)] indicate that the Pt⋅⋅⋅Pt orbital interaction increases the nucleophilicity of the outer dz2
orbitals to provide assembly with electrophilic species. Complexes 1–3 were co‐crystallized with bifunctional halogen bonding (XB) donors to give adducts (1–3)2⋅(1,4‐diiodotetrafluorobenzene) and infinite polymeric [1⋅1,1′‐diiodoperfluorodiphenyl]n. X‐ray crystallography revealed that the supramolecular assembly is achieved through (Aryl)I⋅⋅⋅dz2
[PtII] XBs between iodine σ‐holes and lone pairs of the positively charged (PtII)2 centers acting as nucleophilic sites. The polymer includes a curved linear chain ⋅⋅⋅Pt2⋅⋅⋅I(areneF)I⋅⋅⋅Pt2⋅⋅⋅ involving XB between iodine atoms of the perfluoroarene linkers and (PtII)2 moieties. The 195Pt NMR, UV/Vis, and CV studies indicate that XB is preserved in CH(D)2Cl2 solutions.
The nature and structure of occupied and empty valence electronic states (molecular orbitals, MOs) of the [Ni(Salen)] molecular complex (NiO2N2C16H14) have been studied by means of X-ray photoemission and absorption...
Redox‐active nitroxyl‐containing polymers are promising candidates as possible replacements for inorganic based energy‐storage materials, due to their high energy density and fast redox kinetics. One challenge towards the implementation of such a system is the insufficient electrical conductivity, impeding the charge collection even with highly conductive additives. Herein, the first implementation of a polymeric bis(salicylideniminato) nickel (NiSalen) conductive backbone as an active charge‐collecting wire is reported. NiSalen simultaneously serves as a charge collector for nitroxyl pendants and supports the redox capacity of the material. This novel polymer exhibits a specific capacity of up to 91.5 mAh g−1, retaining 87 % of its theoretical capacity at 800 C and more than 30 % at as high as 3000 C (66 % capacity retention after 2000 cycles). The properties of the new material upon operation was studied by means of operando electrochemical methods, UV‐Vis, and electron paramagnetic resonance spectroscopy.
The
half-lantern PdII
2 complexes trans-(O,C)-[Pd(ppz)(μ-O∩N)]2 (1) and trans-(E,N)-[Pd(ppz)(μ-E∩N)]2 (E∩N is a deprotonated 2-substituted
pyridine; E = S (2), Se (3); Hppz = 1-phenylpyrazole)
were cocrystallized with 1,4-diiodotetrafluorobenzene (FIB) to give
cocrystals 1·(FIB) and (2−3)·2(FIB); the parent complexes and the cocrystals were
studied by X-ray crystallography. The crystal structure of trans-(O,C)-1·FIB is assembled mainly by the I···O halogen
bonding (XB) to give the [@PdII
2]O···I(areneF)I···O[@PdII
2] linkage,
while trans-(E,N)-(2–3)·2(FIB) are built by
the joint action of I···Pd and I···E
XBs, thus furnishing the PdII
2···I(areneF)I···E[@PdII
2] (E = S,
Se) cluster. Detailed theoretical (DFT) studies with the application
of the QTAIM, ELF, NBO, IGM, SAPT, and HSAB methods revealed several
types of attractive noncovalent interactions in the cocrystals, namely,
the I···Pd, I···E (E = O, S, Se), I···C,
π–π-stacking, and π···F interactions.
I···Pd is a rare type of XB involving the metal center
as an XB acceptor, the Pd···Pd communication facilitating
the I···Pd bonding. The I···Pd and I···E
bonds are comparable in strength (the bond interaction energies being
between −7 and −13 kcal/mol), but the former is controlled
by dispersion forces, while the latter is mostly governed by an electrostatic
term.
The improved ORR performance is attributed to the rich density of the Fe–Nx moieties derived from regulated coordination structures using dual-nitrogen-sources.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.