This comprehensive review describes the fullerenes reported in perovskite solar cells since the first report in 2013.

Since the advent of organotransuranium chemistry six decades ago, structurally verified complexes remain restricted to π-bonded carbocycle and σ-bonded hydrocarbyl derivatives. Thus, transuranium-carbon multiple or dative bonds are yet to be reported. Here, utilizing diphosphoniomethanide precursors we report the synthesis and characterization of transuranium-carbene derivatives, namely, diphosphonio-alkylidene- and N -heterocyclic carbene–neptunium(III) complexes that exhibit polarized-covalent σ 2 π 2 multiple and dative σ 2 single transuranium-carbon bond interactions, respectively. The reaction of [Np III I 3 (THF) 4 ] with [Rb(BIPM TMS H)] (BIPM TMS H = {HC(PPh 2 NSiMe 3 ) 2 } 1– ) affords [(BIPM TMS H)Np III (I) 2 (THF)] ( 3Np ) in situ, and subsequent treatment with the N -heterocyclic carbene {C(NMeCMe) 2 } (I Me4 ) allows isolation of [(BIPM TMS H)Np III (I) 2 (I Me4 )] ( 4Np ). Separate treatment of in situ prepared 3Np with benzyl potassium in 1,2-dimethoxyethane (DME) affords [(BIPM TMS )Np III (I)(DME)] ( 5Np , BIPM TMS = {C(PPh 2 NSiMe 3 ) 2 } 2– ). Analogously, addition of benzyl potassium and I Me4 to 4Np gives [(BIPM TMS )Np III (I)(I Me4 ) 2 ] ( 6Np ). The synthesis of 3Np – 6Np was facilitated by adopting a scaled-down prechoreographed approach using cerium synthetic surrogates. The thorium(III) and uranium(III) analogues of these neptunium(III) complexes are currently unavailable, meaning that the synthesis of 4Np – 6Np provides an example of experimental grounding of 5f- vs 5f- and 5f- vs 4f-element bonding and reactivity comparisons being led by nonaqueous transuranium chemistry rather than thorium and uranium congeners. Computational analysis suggests that these Np III =C bonds are more covalent than U III =C, Ce III =C, and Pm III =C congeners but comparable to analogous U IV =C bonds in terms of bond orders and total metal contributions to the M=C bond...

Utilizing the bulky guanidinate ligand [L] (L = (Ar*N)C(R), Ar* = 2,6-bis(diphenylmethyl)-4-tert-butylphenyl, R = NCBu) for kinetic stabilization, the synthesis of a rare terminal Fe(IV) nitride complex is reported. UV irradiation of a pyridine solution of the Fe(II) azide [L]FeN(py) (3-py) at 0 °C cleanly generates the Fe(IV) nitride [L]FeN(py) (1). The N NMR spectrum of the 1 (50% Fe≡N) isotopomer shows a resonance at 1016 ppm (vs externally referenced CHNO at 380 ppm), comparable to that known for other terminal iron nitrides. Notably, the computed structure of 1 reveals an iron center with distorted tetrahedral geometry, τ = 0.72, featuring a short Fe≡N bond (1.52 Å). Inspection of the frontier orbital ordering of 1 shows a relatively small HOMO/LUMO gap with the LUMO comprised by Fe(d)N(p) π*-orbitals, a splitting that is manifested in the electronic absorption spectrum of 1 (λ = 610 nm, ε = 1375 L·mol·cm; λ = 613 nm (calcd)). Complex 1 persists in low-temperature solutions of pyridine but becomes unstable at room temperature, gradually converting to the Fe(II) hydrazide product [κ-(BuCN)C(η-NAr*)(N-NAr*)]Fe (4) upon standing via intramolecular N-atom insertion. This reactivity of the Fe≡N moiety was assessed through molecular orbital analysis, which suggests electrophilic character at the nitride functionality. Accordingly, treatment of 1 with the nucleophiles PMePh and Ar-N≡C (Ar = 2,6-dimethylphenyl) leads to partial N-atom transfer and formation of the Fe(II) addition products [L]Fe(N═PMePh)(py) (5) and [L]Fe(N═C═NAr)(py) (6). Similarly, 1 reacts with PhSiH to give [L]Fe[N(H)(SiHPh)](py) (7) which Fukui analysis shows to proceed via electrophilic insertion of the nitride into the Si-H bond.

Background: Advanced glycation end products (AGEs) have been linked to pathogenic mechanisms of diabetes mellitus. However, little is known about the contribution of protein glycation to periodontal disease in patients with diabetes. Therefore, this study investigated whether glycation of type I collagen (COLI) and fibronectin (FN) modified the behavior of human gingival fibroblasts (hGF) and periodontal ligament fibroblasts (hPDL).