2-substituted-1-amino-o-carboranes 2-R-1-NH_(2)-o-C_(2)B_(10)H_(10)(R=CH_(3),1a;R=Ph,1b)were synthesized and the reactions of these compounds with the yttrium dialkyl complex[Y(L)(CH_(2)SiMe3)_(2)](L=[2-(2,5-Me_(2)C_(...2-substituted-1-amino-o-carboranes 2-R-1-NH_(2)-o-C_(2)B_(10)H_(10)(R=CH_(3),1a;R=Ph,1b)were synthesized and the reactions of these compounds with the yttrium dialkyl complex[Y(L)(CH_(2)SiMe3)_(2)](L=[2-(2,5-Me_(2)C_(4)H_(2)N)C_(6)H4NC(Ph)=NDipp]-,Dipp=2,6-iPr_(2)C_(6)H_(3))were investigated.The 1H NMR spectroscopy indicate that the reaction of ytrrium dialkyl complex with one equivalent of 2-R-1-NH_(2)-o-C_(2)B_(10)H_(10) produce the mixture of ytrrium alkyl-amido complex[Y(L)(2-R-1-NH-o-C_(2)B_(10)H_(10))(CH_(2)SiMe3)](R=CH_(3),2a;R=Ph,2b)and bis(amido)complex[Y(L)(2-R-1-NH-o-C_(2)B_(10)H_(10))_(2)](R=CH_(3),3a;R=Ph,3b).The yttrium bridging imido complex[Y(L)(2-CH_(3)-1-N-o-C_(2)B_(10)H_(10))]_(2)(4a)was obtained by heating the mixture at 55℃for 12 h.Complex 3a was isolated and characterized by treating the yttrium dialkyl complex with two equivalents of 1a.The structures of complexes 3a and 4a were verified by single-crystal Xray diffraction.CCDC:2424136,3a;2424137,4a.展开更多
A facile access to mono-C-alkynyl-o-carboranes from o-carboranes and arylsulfonylacetylenes was developed.This facile process tolerates a wide variety of functional groups,occurs at mild conditions in onepot procedure...A facile access to mono-C-alkynyl-o-carboranes from o-carboranes and arylsulfonylacetylenes was developed.This facile process tolerates a wide variety of functional groups,occurs at mild conditions in onepot procedure with short reaction time.The obtained mono-C-alkynyl-o-carboranes can be easily derivatized to synthesize 1,2-difunctionalized o-carboranes.This work provides a useful tool for the functionalization of o-carboranes.展开更多
How long a C-C bond can be?A question has long fascinated chemists.This work reports an example of extraordinary long C-C bond distance of 1.990(4)?observed in single-crystal X-ray structure of 1,2-(NHMes)2-o-carboran...How long a C-C bond can be?A question has long fascinated chemists.This work reports an example of extraordinary long C-C bond distance of 1.990(4)?observed in single-crystal X-ray structure of 1,2-(NHMes)2-o-carborane(2;Mes=2,4,6-trimethylphenyl).DFT calculations show that hyperconjugation of lone pairs of the nitrogen atoms into the emptyσ^*orbital of the cage C-C bond is the origin of the bond elongation.Such hyperconjugation can be suppressed if the two nitrogen atoms in 2 are linked to a Lewis acidic germanium(Ⅱ)center.展开更多
Two o-carborane based tetraphenylethene(TPE)cationic cyclophanes O1.4PF_(6)and O2.4PF_(6)were syn thesized through an S_(N)2 reaction.Their structures were confirmed both possessing Z-shaped cavities in single crystal...Two o-carborane based tetraphenylethene(TPE)cationic cyclophanes O1.4PF_(6)and O2.4PF_(6)were syn thesized through an S_(N)2 reaction.Their structures were confirmed both possessing Z-shaped cavities in single crystal analysis.The optical properties of these macrocycles were systematically investigated using UV–vis spectroscopy and fluorescence techniques.It is worth noting that the introduction of a methoxy group to the TPE unit enables the synthesis of a near-infrared-emitting macrocycle O2.4PF_(6).The recogni tion behaviors of these two macrocycles towards nucleotides were investigated using various technique including fluorescence titration,UV–vis titration,and transmission electron microscopy(TEM).Interest ingly,these cyclophanes exhibited aggregation-induced emission(AIE)effects in water or under the in duction of nucleotides.展开更多
Based on three rationally designed pyrrole-appended o-carborane derivatives,we present that fluores-cence properties of crystalline materials are highly dependent on intermolecular interaction and steric hinderance.Th...Based on three rationally designed pyrrole-appended o-carborane derivatives,we present that fluores-cence properties of crystalline materials are highly dependent on intermolecular interaction and steric hinderance.Though the three molecules are similar in structure,single crystals of the three compounds showed obvious difference in molecular stacking and fluorescence behavior.Systematic studies indicate that fluorescence quantum yields,thermo-response as well as mechano-response are highly dependent on intermolecular interaction and steric hindrance.In the three crystalline materials,the CB-NMe crys-tals with weaker intermolecular interaction and looser molecular packing showed superior fluorescence quantum yield and temperature sensitivity.Accordingly,surface temperature detection strip with favor-able reversibility is prepared by doping CB-NMe into the polymer.In addition,the CB-NMe aggregates can be used for monitoring bovine serum albumin(BSA)denaturation,as temperature response of the aggregates can be reversed when co-assembled with BSA.展开更多
Innovative design of sensing fluorophores possessing superior photophysical properties,porosity,and packing-resistance structures is pivotal for high performance film-based fluorescent sensors.Herein,PDCB,a perylene m...Innovative design of sensing fluorophores possessing superior photophysical properties,porosity,and packing-resistance structures is pivotal for high performance film-based fluorescent sensors.Herein,PDCB,a perylene monoimide(PMI)derivative incorporating large spatial phenyl-carborane was synthesized and found to exhibit unexpected photophysical properties.The structurally bent PDCB exhibits not only PMI-like emission but also a red-shifted emission.In sharp contrast,PMI-CBH,a linear PMI derivative,exhibits only PMI-like emission.Furthermore,upon local excitation,PDCB undergoes a photoinduced electron transfer(PET)between PMI and phenylcarborane,resulting in a charge-transfer state.Two other PMI derivatives,PCB and PDCBP,showed a similar phenomenon.The PET rate is in the order of PCB(48 ps^(-1))>PDCB(163 ps^(-1))>PDCBP(815 ps^(-1))in toluene,which decreases with increasing steric hindrance,inferring structure reorganization prior to the PET process.As expected,a fabricated PDCB-based sensor showed excellent performance in acetone sensing.展开更多
Reactions of [Cp2Ln(μ-Cl)]2 (Cp= η5-C5H5, Ln = Nd, Yb, Dy, Gd, Er) with an equivalent of [(THF)3LiE2C2Bi0H10Li. (THF)]2 (E= S, Se) in THF afforded the dinuclear sandwich complexes of formula [CP2LnE2C2B10H10]2[LI(TH...Reactions of [Cp2Ln(μ-Cl)]2 (Cp= η5-C5H5, Ln = Nd, Yb, Dy, Gd, Er) with an equivalent of [(THF)3LiE2C2Bi0H10Li. (THF)]2 (E= S, Se) in THF afforded the dinuclear sandwich complexes of formula [CP2LnE2C2B10H10]2[LI(THF)4]2[E = S, Ln=Nd (1a), Yb (2a), Dy (3a), Gd (4a), Er (5a); E=Se, Ln=Nd (1b), Yb (2b), Dy (3b), Gd (4b), Er (5b)]. The molecular structures of complexes la, 2a and 2b were determined by the single crystal X-ray structure analyses. Two lanthanide atoms are connected by a pair chalcogen (η1, η2-E2C2B10H10) bridging ligands and the central Ln2E2 four membered ring is not planar.展开更多
文摘2-substituted-1-amino-o-carboranes 2-R-1-NH_(2)-o-C_(2)B_(10)H_(10)(R=CH_(3),1a;R=Ph,1b)were synthesized and the reactions of these compounds with the yttrium dialkyl complex[Y(L)(CH_(2)SiMe3)_(2)](L=[2-(2,5-Me_(2)C_(4)H_(2)N)C_(6)H4NC(Ph)=NDipp]-,Dipp=2,6-iPr_(2)C_(6)H_(3))were investigated.The 1H NMR spectroscopy indicate that the reaction of ytrrium dialkyl complex with one equivalent of 2-R-1-NH_(2)-o-C_(2)B_(10)H_(10) produce the mixture of ytrrium alkyl-amido complex[Y(L)(2-R-1-NH-o-C_(2)B_(10)H_(10))(CH_(2)SiMe3)](R=CH_(3),2a;R=Ph,2b)and bis(amido)complex[Y(L)(2-R-1-NH-o-C_(2)B_(10)H_(10))_(2)](R=CH_(3),3a;R=Ph,3b).The yttrium bridging imido complex[Y(L)(2-CH_(3)-1-N-o-C_(2)B_(10)H_(10))]_(2)(4a)was obtained by heating the mixture at 55℃for 12 h.Complex 3a was isolated and characterized by treating the yttrium dialkyl complex with two equivalents of 1a.The structures of complexes 3a and 4a were verified by single-crystal Xray diffraction.CCDC:2424136,3a;2424137,4a.
基金financial support from the National Natural Science Foundation of China(Nos.21672193,21272218)the Key Scientific and Technological Project of Henan Province(No.202102310327)+3 种基金the Ministry of Industry and Information Technology(No.Z135060009002)the Postdoctoral Research Grant in Henan Province(No.001803004)the Programme of Introducing Talents of Discipline to Universities(111 Project,No.D20003)Zhengzhou University of China。
文摘A facile access to mono-C-alkynyl-o-carboranes from o-carboranes and arylsulfonylacetylenes was developed.This facile process tolerates a wide variety of functional groups,occurs at mild conditions in onepot procedure with short reaction time.The obtained mono-C-alkynyl-o-carboranes can be easily derivatized to synthesize 1,2-difunctionalized o-carboranes.This work provides a useful tool for the functionalization of o-carboranes.
基金supported by a grant from the Research Grants Council of the Hong Kong Special Administration Region (No. 14305918)
文摘How long a C-C bond can be?A question has long fascinated chemists.This work reports an example of extraordinary long C-C bond distance of 1.990(4)?observed in single-crystal X-ray structure of 1,2-(NHMes)2-o-carborane(2;Mes=2,4,6-trimethylphenyl).DFT calculations show that hyperconjugation of lone pairs of the nitrogen atoms into the emptyσ^*orbital of the cage C-C bond is the origin of the bond elongation.Such hyperconjugation can be suppressed if the two nitrogen atoms in 2 are linked to a Lewis acidic germanium(Ⅱ)center.
基金supported by the National Natural Science Foundation of China(No.22071025)the Joint Independent Innovation Fund of Tianjin University and Fuzhou University(No.TF2021-3)the Young and Middle-aged Teacher Education Research Project of Fujian Province(No.JAT210020)。
文摘Two o-carborane based tetraphenylethene(TPE)cationic cyclophanes O1.4PF_(6)and O2.4PF_(6)were syn thesized through an S_(N)2 reaction.Their structures were confirmed both possessing Z-shaped cavities in single crystal analysis.The optical properties of these macrocycles were systematically investigated using UV–vis spectroscopy and fluorescence techniques.It is worth noting that the introduction of a methoxy group to the TPE unit enables the synthesis of a near-infrared-emitting macrocycle O2.4PF_(6).The recogni tion behaviors of these two macrocycles towards nucleotides were investigated using various technique including fluorescence titration,UV–vis titration,and transmission electron microscopy(TEM).Interest ingly,these cyclophanes exhibited aggregation-induced emission(AIE)effects in water or under the in duction of nucleotides.
基金funding from the Natural Science Foundation of China (Nos. 22072084, 21820102005)111 Project (No. B14041)+1 种基金the Fundamental Research Funds for the Central Universities (Nos. GK202103048, GK202001005, 2020CSLY008)the Innovation Capability Support Program of Shaanxi (No. 2021TD-18)
文摘Based on three rationally designed pyrrole-appended o-carborane derivatives,we present that fluores-cence properties of crystalline materials are highly dependent on intermolecular interaction and steric hinderance.Though the three molecules are similar in structure,single crystals of the three compounds showed obvious difference in molecular stacking and fluorescence behavior.Systematic studies indicate that fluorescence quantum yields,thermo-response as well as mechano-response are highly dependent on intermolecular interaction and steric hindrance.In the three crystalline materials,the CB-NMe crys-tals with weaker intermolecular interaction and looser molecular packing showed superior fluorescence quantum yield and temperature sensitivity.Accordingly,surface temperature detection strip with favor-able reversibility is prepared by doping CB-NMe into the polymer.In addition,the CB-NMe aggregates can be used for monitoring bovine serum albumin(BSA)denaturation,as temperature response of the aggregates can be reversed when co-assembled with BSA.
基金the Ministry of Science and Technology of China(grant nos.SQ2022YFA1200081 and 2022010133)the National Natural Science Foundation of China(grant nos.21820102005 and 22132002)111 project(grant no.B14041).
文摘Innovative design of sensing fluorophores possessing superior photophysical properties,porosity,and packing-resistance structures is pivotal for high performance film-based fluorescent sensors.Herein,PDCB,a perylene monoimide(PMI)derivative incorporating large spatial phenyl-carborane was synthesized and found to exhibit unexpected photophysical properties.The structurally bent PDCB exhibits not only PMI-like emission but also a red-shifted emission.In sharp contrast,PMI-CBH,a linear PMI derivative,exhibits only PMI-like emission.Furthermore,upon local excitation,PDCB undergoes a photoinduced electron transfer(PET)between PMI and phenylcarborane,resulting in a charge-transfer state.Two other PMI derivatives,PCB and PDCBP,showed a similar phenomenon.The PET rate is in the order of PCB(48 ps^(-1))>PDCB(163 ps^(-1))>PDCBP(815 ps^(-1))in toluene,which decreases with increasing steric hindrance,inferring structure reorganization prior to the PET process.As expected,a fabricated PDCB-based sensor showed excellent performance in acetone sensing.
基金theNationalNaturalScienceFoundationofChina (No .2 992 5 10 1)andtheMajorStateBasicResearchDevelop mentProgramofChina (No .G19990 6 480 0 )
文摘Reactions of [Cp2Ln(μ-Cl)]2 (Cp= η5-C5H5, Ln = Nd, Yb, Dy, Gd, Er) with an equivalent of [(THF)3LiE2C2Bi0H10Li. (THF)]2 (E= S, Se) in THF afforded the dinuclear sandwich complexes of formula [CP2LnE2C2B10H10]2[LI(THF)4]2[E = S, Ln=Nd (1a), Yb (2a), Dy (3a), Gd (4a), Er (5a); E=Se, Ln=Nd (1b), Yb (2b), Dy (3b), Gd (4b), Er (5b)]. The molecular structures of complexes la, 2a and 2b were determined by the single crystal X-ray structure analyses. Two lanthanide atoms are connected by a pair chalcogen (η1, η2-E2C2B10H10) bridging ligands and the central Ln2E2 four membered ring is not planar.
