Dicyclohexylcarbodiimide (DCC) or diisopropylcarbodiimide (DIC) was nucleophilically added to lithium amides containing TMS-Apy/Apy, and then further reacted with different metal chlorides to obtain complexes with various coordination modes. Reaction with CoCl2 or FeCl2 led to guanidinate-containing unsymmetric 1, 3, 5-triazapentadiene ligands complexes [{CyNC{N(H)Cy}NPy}(2)Co] (1), [{CyNC{N(SiMe3)Cy}NPy}(2)Co] (2a), and [{CyNC{N(SiMe3)Cy}NPy}(2)Fe] (2b). Reaction with MnCl2 yielded a Li-Mn bimetallic complex [{CyNC{N(SiMe3)Cy}NPy}(3)LiMn] (3) with both amidinate and guanidinate structures. Additionally, a 1, 3-SiMe3/-H migration usually occurs during the insertion of carbodiimide into lithium amide. However, when DIC was used for nucleophilic addition and followed by a reaction with SnCl2, only a four-coordinated guanidinate complex [{iPrNC(NiPr)N{(SiMe3)Py}}(2)Sn] (4) without -SiMe3 shift was obtained.

Herein a novel and robust methodology to spiroimidazolidinones has been developed under a mild reaction. The reaction of (Z)-2-azido-3-phenylacrylic acids 1, aldehydes 2, amines 3, isocyanides 4, and isocyanides 6 produced regioselectively spiroimidazolidinones in 71-88% yields via a sequential Ugi 4CR/Pd(0) catalyzed azide-isocyanide coupling/cyclization/rearrangement/hydroxylation reaction. Furthermore, the easily accessible starting materials, high bond-forming efficiency, and broad substituent tolerance make this strategy useful in synthetic and medicinal chemistry.

Three bisferrocene-based bis(acylthiourea) positional isomers, namely, 1,2-bis(ferrocenylcarbonylthioureido)benzene (1), 1,3-bis(ferrocenylcarbonylthioureido)benzene (2) and 1,4-bis(ferrocenylcarbonylthioureido)benzene (3), all [Fe2(C5H5)2(C20H16N4O2S2)], have been synthesized via facile nucleophilic addition reactions of 2.3 equivalents of ferrocenoyl isothiocyanate with o-, m- and p-phenylenediamine, respectively. The structures of the three new synthesized isomers were fully characterized by 1H NMR, 13C NMR, IR and UV-Vis spectroscopy, elemental analyses and cyclic voltammetry. In addition, the structures of acetone monosolvated compound 1 (1·CH3COCH3), as well as compounds 2 and 3, have been determined by single-crystal X-ray diffraction. A combination of intermolecular N-H...S and C-H...S hydrogen bonds connects the components of compound 1·CH3COCH3 into infinite helix chains. Two pairs of different N-H...S and C-H...S intermolecular hydrogen bonds, as well as N-H...O and C-H...π co-operating interactions, link the molecules of compound 2 into a two-dimensional network. In contrast, compound 3 displays a one-dimensional double-chain array via two intermolecular C-H...S hydrogen bonds. Therefore, the three reported positional isomers present unique individual crystal assemblies.

Unsymmetrical amidinate Co(II) complexes[Co{N(2,6-iPr2C6H3)C(Ph)N(SiMe3)}2] (1,1a) and Mn(II) complex [Mn{N(2,6-iPr2C6H3)C(Ph)N(SiMe3)}2PhCN] (3) were synthesized and characterized. Their single crystal X-ray diffraction results were presented to analyze the differences in crystal formation. These complexes were used as catalyst in the addition reaction of aromatic amines with N,N'-diisopropylcarbodiimide. Complex 1 exhibits relatively higher catalytic activity. Especially in the addition reaction of 2,6-diisopropylaniline, which has large steric hindrance, with N,N'-diisopropylcarbodiimide in THF solvent, the catalyzed yield could be up to 99 %.

Four Ru(II)-centered isomeric complexes [RuCl(5cqn)(Val)(NO)] (1-4) were synthesized with 5cqn (5-chloro-8-hydroxyquinoline) and chiral Val (Val = L- or D-valine) as co-ligand, and their structures were confirmed using the X-ray diffraction method. The cytotoxicity and photodynamic activity of the isomeric complexes and their human serum albumin (HSA) complex adducts were evaluated. Both the isomeric complexes and their HSA complex adducts significantly affected HeLa cell proliferation, with an IC50 value in the range of 0.3-0.5 mu M. The photo-controlled release of nitric oxide (NO) in solution was confirmed using time-resolved Fourier transform infrared and electron paramagnetic resonance spectroscopy techniques. Furthermore, photoinduced NO release in living cells was observed using a selective fluorescent probe for NO. Moreover, the binding constants (Kb) of the complexes with HSA were calculated to be 0.17-1.98 x 104 M-1 and the average number of binding sites (n) was found to be close to 1, it can serve as a crucial carrier for delivering metal complexes. The crystal structure of the HSA complex adduct revealed that one [RuCl(H2O)(NO)(Val)]+ molecule binds to a pocket in domain I. This study provides insight into possible mechanism of metabolism and potential applications for nitrosylruthenium complexes. Graphical Abstract Structure, anti-proliferation activity and photoinduced NO release of four nitrosylruthenium isomeric complexes and their HSA complex adducts.

Thermally activated delayed fluorescence (TADF) emitters with aggregation-enhanced emission (AEE) characteristics are in high demand in organic light-emitting diodes (OLEDs) because of their strong fluorescence and high exciton utilization under electrical excitation. In this work, an AEE-active TADF emitter, 10,10'-(5-((9phenyl-9H-carbazol-3-yl)sulfonyl)-1,3-phenylene)bis(9,9-dimethyl-9,10-dihydroacridine) (CZ-DPS-BAD), adopting diphenylsulfone skeleton as electron-accepting segment and 9-phenylcarbazole and 9,9-dimethyl-9,10-dihydroacridine as electron donors is developed. The small singlet-triplet splitting (0.13 eV) and high photoluminescence quantum yield (82 %) of CZ-DPS-BAD can attribute to the formation of large dihedral angles between electron donor-acceptors and weak electron-exchange interaction that suppress concentration quenching and exciton annihilation. The assigned characteristics result in reverse intersystem crossing rate of up to 5.0 x 10(5) s(-1) and a delayed fluorescence lifetime of 5.3 mu s. Notably, CZ-DPS-BAD behaves excellent non-doped OLED performance with the emission peak of 486 nm, the maximum current efficiency of 47.4 cd/A, the maximum power efficiency of 46.1 lm W-1, the maximum external quantum efficiency of 20.3 %, and the exciton utilizin efficiency of 83 %. It was also found that the short delayed fluorescence lifetime impair the triplet exciton annihilation resulting small efficiency roll-off in OLED. This work provides a general approach to explore new efficient and stable emitters by rationally regulating intermolecular interactions and integrating AEE and TADF, which facilitates their applications in optoelectronics.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

We report on the synthesis of a cage-type calix[4]pyrrole (1) bearing an additional basic pyridinebisthiazolamine group on the strap. The receptor in its protonated form shows strong affinity and selectivity for sulfate over a wide range of inorganic anions. With receptor 1 as a liquid-liquid extractant, H+/SO42- in the form of H2SO4 is almost quantitatively extracted from an aqueous solution containing HNO3 at a high concentration to CH2Cl2 in a recyclable manner.

Lithium amidinates or guanidinates form novel complexes 1–4 with N,N′-dicyclohexylcarbodiimide (CyN=C=NCy, DCC) or N,N′-diisopropylcarbodiimide ( i PrN=C=N i Pr, DIC). Their structures were characterized by spectroscopic and X-ray crystallographic method. The X-ray diffraction analysis revealed that heteroleptic complexes 1–3 were mononuclear with a four-co-ordinate metal center and homoleptic 4 was dimeric. Both the W-shaped 1,3,5-triazapentadienato lithium 1–3 and U-shaped 4 could be regarded as good intermediates en route to their metal complexes with varied substrates.

Insertion of 2,6-iPr2C6H3N(Li)SiMe3 or PhN(Li)SiMe3 to the CN bond of Me2NCN or PhCN afforded the lithium complexes [Li(2,6-iPr2C6H3)NC(NMe2)NC(NMe2)N(SiMe3)]2 (1a) and [Li(PhNC(Ph)NSiMe3)]2 (1b). Complexes 1a and 1b were used as precursors to react with AlCl3 affording [(2,6-iPr2C6H3)NC(NMe2)NC(NMe2)N(SiMe3)]2AlCl (2) and [(PhNC(Ph)NSiMe3)]2AlCl (3), respectively. The structures of 2 and 3 were presented. Both 2 and 3 exhibit good activity to catalyze the addition reaction of arylamines to N,N'-diisopropylcarbodiimide.

The determination and quantification of oxidants related with chemical engineering and chemical industry is always an important issue for modern analytical chemistry. In this paper, a series of electron-rich ligands were synthesized and confirmed by their single crystals. Their cyclic voltammetry curves suggested that they were sensitive towards oxidants. These electron-rich ligands were coordinated with Eu(III) and Tb(III) ions and doped into a MOF (metal-organic-framework) supporting matrix of bio-MOF-1. Here bio-MOF-1 denoted [Zn-8(ad)(4)(BPDC)(6)O center dot 2(M(e)2NH(2))(+)]center dot G, ad = adenine, BPDC = 4,4'-biphenyl dicarboxylic acid, G = N,N-dimetylformamide and water. The resulting composite sample was analyzed and confirmed with SEM, XRD, N-2 adsorption/desorption and ICP measurement. It was found that there was an energy competing between Eu(III) and Tb(III) emissive centers. The Eu(III) emission intensity was decreased with increasing peracitic acid concentration, but the Tb(III) emission intensity was increased, showing ratiometric sensing signal. Linear sensing behavior was observed with sensitivity as high as 8.01 and response time of similar to 93 s. The sensing mechanism was revealed as the energy competing between Eu(III) and Tb(III) ions. In the absence of peracitic acid, the dominant energy transfer was a Eu(III)-based one, showing strong Eu(III) emission and weak Tb(III) emission. After adding peracitic acid, ligand energy transfer for Tb(III) was enhanced but that for Eu(III) was compromised, leading to quenched Eu(III) emission and increased Tb(III) emission. A good sensing selectivity was observed and attributed to the protecting and buffering effect of supporting matrix bio-MOF-1.

Seven examples of chlorozirconium N‐[(N,N‐dimethylamino)dimethylsilyl]‐2‐pyridylaminates, mononuclear monoligand Zr[(RC5H4N)NSiMe2NMe2]Cl3LiCl(Et2O)2 (R = 4‐Me, Zr1; R = 5‐Me, Zr2; R = 5‐Cl, Zr3), chloro‐bridged dinuclear diligand [Zr{(RC5H4N)NSiMe2NMe2}Cl3]2 (R = 5‐Cl, Zr4; R = 4‐Cl, Zr5), and mononuclear triligand Zr[(RC5H4N)NSiMe2NMe2]3Cl (R = 6‐Me, Zr6; R = H, Zr7), have been prepared by the individual reactions of zirconium tetrachloride with the corresponding lithium N‐[(N,N‐dimethylamino)dimethylsilyl]‐2‐pyridylaminates of (RC5H4N)NHSiMe2NMe2 (R = 4‐Me, 1a; 5‐Me, 1b; 5‐Cl, 1c; 4‐Cl, 1d; 6‐Me, 1e; H, 1f), respectively. Besides seven coordination around zirconium core, Zr1–Zr5 adopt a distorted pentagonal bipyramid geometry with the ligand acting as a monoanionic η2:η1‐tridentate fashion; Zr6–Zr7 present capped trigonal prism geometry with the ligand as η2‐coordination with a pendant N (CH3)2 free. Extensively, the reactions of FeCl2 with lithiated (RC5H4N)NHSiMe2NMe2 (R = 4‐Me, 1a; 5‐Cl, 1c; 6‐Me, 1e) afford the corresponding dimeric complexes (R = 4‐Me, Fe1; 5‐Cl, Fe2; 6‐Me, Fe3), in which Fe1 and Fe2 exhibit C2 symmetry with each iron unit as a distorted trigonal bipyramidal geometry, while Fe3 specially possesses a centrosymmetric hour‐glass‐shaped core with each iron center as a distorted tetrahedral geometry. Upon activation with methylaluminoxane (MAO), zirconium complexes exhibit moderate to good activities toward ethylene polymerization and produce the polyethylenes with high molecular weight and broad dispersity.

Abstract C32H54Li2N4Si2, monoclinic, P21/n (no. 14), a = 11.611(4) Å, b = 11.157(6) Å, c = 13.307(5) Å, β = 100.12(3)°, V = 1697.0(12) Å3, Z = 2, Rgt(F) = 0.0622, wRref(F2) = 0.1561, T = 213 K.

Abstract Zn(C15H24NSi)2, triclinic, P1‾$P‾{1}$ (no. 2), a = 8.828(3) Å, b = 9.458(3) Å, c = 10.786(3) Å, α = 74.609(4)°, β = 73.915(4)°, γ = 64.888(4)°, V = 772.1(4) Å3, Z = 1, Rgt(F) = 0.0476, wRref(F2) = 0.1225, T = 293 K.

Abstract C56H60N8O4Zr, monoclinic, C2/c (no. 15), a = 24.665(4) Å, b = 18.836(3) Å, c = 25.425(6) Å, β = 114.364(4)°, V = 10760(4) Å3, Z = 8, Rgt(F) = 0.0550, wRref(F2) = 0.1239, T = 296(2) K.

本研究发明了一种新型秸秆碳复合材料制备方法,并将其成功应用在了养殖业废水处理过程中.本文首先介绍了新型秸秆碳复合材料的制备方法,然后介绍了复合材料在养殖业废水处理中的应用,并对其工艺和应用的优势点进行了分析.最后对废水的再利用问题进行了研究,根据废水的处理阶段,介绍了废水的具体再利用方法.

A pentanuclear Sn(II) guanidinate complex [PhNC(NMe)(2)N(H)SnCl](2)[PhNC(NMe)(2)NSnCl](2)Sn (1) was synthesized via the reaction of PhN(Li)SiMe3 and anhydrous tin(II) chloride. It was well structurally characterized by H-1 NMR, C-13 NMR, elemental analysis, and X-ray single crystal crystallography techniques. Complex 1 is an active catalyst in the addition reaction of arylamines into N,N'-diisopropylcarbodiimide giving guanidinates.

Mononuclear zirconium complex 3a of the molecular identity [Zr[ η 2 ‐(C 4 H 3 O)C (Et) = NNPh]Cl 3 (THF) 2 ], dinuclear zirconium complexes 3b [{Zr[ η 2 ‐(C 4 H 3 O)C( i ‐Pr) = NNPh] 2 } 2 ( μ 2 ‐Cl) 3 ( μ 3 ‐Cl) 2 Li(Et 2 O)] and 3c [{Zr[ η 2 ‐(C 4 H 3 O)C( t ‐Bu) = NNPh] 2 } 2 Cl 2 ( μ 2 ‐Cl) 2 ] have been synthesized by the treatment of lithium salt of (C 4 H 3 O)C(R) = NNHPh (R = CH 3 CH 2 , 1a ; R = (CH 3 ) 2 CH, 1b ; R = (CH 3 ) 3 C, 1c ), with different molar ratios of anhydrous zirconium tetrachloride. Of these, complex 3b was formed with lithium adduct and no such adduct was found in complex 3c . Compound 1a and all the zirconium complexes ( 3a ‐ 3c ) were structurally characterized by single‐crystal X‐ray diffraction studies. Thus, it revealed that each hydrazonato ligand acts in a strained η 2 ‐coordination fashion for the three zirconium complexes. The molecular structures of the three zirconium complexes ( 3a ‐ 3c ) reveal the existence of intramolecular hydrogen bonding interactions. Interestingly, complexes 3a and 3b assemble into a two‐dimensional network structure through intermolecular hydrogen‐bonding interactions. Upon activation with methylaluminoxane (MAO), all the complexes namely 3a , 3b , and 3c exhibited moderate catalytic activities toward ethylene polymerization and produced high molecular weight polyethylene with narrow molecular weight distributions.

Two bulky three-coordinate tin(II) complexes 1 and 2 have been prepared: [N(Ar)C(R)NC(R)N(R')]SnCl (Ar = 2,6-(Pr2C6H3)-Pr-i, R = NMe2, R' = H, 1; R = 1-piperidino, R' = SiMe3, 2). Their single-crystal X-ray diffraction studies are presented. They can be used as efficient pre-catalysts for catalytic addition of arylamines to N,N'-diisopropylcarbodiimide. (C) 2020 Elsevier Ltd. All rights reserved.