This Special Issue serves as the proceedings for the 19th International Symposium on Small Particles and In- organic Clusters (ISSPIC XIX), held in Hangzhou, China from August 12-17, 2018. All the articles represent o...This Special Issue serves as the proceedings for the 19th International Symposium on Small Particles and In- organic Clusters (ISSPIC XIX), held in Hangzhou, China from August 12-17, 2018. All the articles represent orig- inal research and are peer-reviewed.展开更多
Polyhedral boranes are a class of well-known boron molecular clusters with unique physical and chemical properties,and great efforts have been made in the past decades to find more effective synthetic methods.However,...Polyhedral boranes are a class of well-known boron molecular clusters with unique physical and chemical properties,and great efforts have been made in the past decades to find more effective synthetic methods.However,the established synthetic methods suffer from low efficiency and low selectivity because the mechanism of the B-H bond condensation reaction,critical for the synthesis of the polyhedral boranes,is not well understood.Here we report highly selective and efficient synthetic methods of the salts of the tetradecahydridoundecaborate(1-)(B_(11)H^(-)_(14)) and dodecahydrido-dodecaborates(2-)(B_(12)H_(12)^(2-)) anions by employing commercially available and inexpensive starting materials.Both theoretical and experimental investigations are carried out to elucidate the reaction mechanisms.We have found that the nature of the B-H bond condensation is the dihydrogen bonding interaction in which the positively charged hydrogens(bridged hydrogens) play a crucial role.The current study has not only led to more effective and selective synthetic methods for B_(11)H^(-)_(14) and B_(12)H_(12)^(2-) but also unveiled the nature of the B-H bond condensation and the general formation mechanisms of polyhedral boranes.This finding will facilitate the development of more effective synthetic methods for polyhedral boranes and spur their wide application.展开更多
Valence-bound molecular anions with polar neutral cores(μ>2.5 D)can support highly diffuse dipole-bound states(DBSs)as electronically excited states just below the detachment threshold.Such weakly bound nonvalence...Valence-bound molecular anions with polar neutral cores(μ>2.5 D)can support highly diffuse dipole-bound states(DBSs)as electronically excited states just below the detachment threshold.Such weakly bound nonvalence excited states have little influence on the structure of the neutral core,and they usually have the same vibrational frequencies.DBSs can be systematically searched using photodetachment spectroscopy(PDS),which can yield the binding energies of the DBSs,the electron detachment threshold of the anion,and above-threshold vibrational levels of the DBSs(Feshbach resonances).We have shown that the combination of PDS and resonant photoelectron spectroscopy(rPES)at the Feshbach resonances is a powerful approach to obtain rich vibrational information for complex molecular radicals.A prerequisite for this technique is to produce vibrationally cold anions,made possible by a cryogenically controlled Paul trap.In this article,we report a PDS and rPES study of cold para-ethylphenolate anions(p-EP^(-)).The electron affinity of the p-EP radical is measured to be 17425±3 cm^(-1)(2.1604±0.0004 eV),and a DBS is found at 145 cm^(-1) below the detachment threshold of p-EP^(-).Thirty-four vibrational levels are observed for the DBS,including two bound levels and 32 Feshbach resonances.Frequencies for 17 vibrational modes of the p-EP radical are measured from the combination of PDS and rPES,including six symmetry-forbidden modes with A″symmetry.The current study confirms again the power of combining cryogenic ion cooling with PDS and highresolution rPES to obtain spectroscopic information on complex molecular radicals.展开更多
基金supported by the National Natural Science Foundation of China (No.21590792, No.91426302, and No.21433005)supported by the U.S. National Science Foundation (CHE-1763380)
文摘This Special Issue serves as the proceedings for the 19th International Symposium on Small Particles and In- organic Clusters (ISSPIC XIX), held in Hangzhou, China from August 12-17, 2018. All the articles represent orig- inal research and are peer-reviewed.
基金supported by the National Natural Science Foundation of China(22171246,U1804253 to X.C.and 21773214 to D.W.)the National Science Foundation(CHE-2053541 to L.-S.W.)。
文摘Polyhedral boranes are a class of well-known boron molecular clusters with unique physical and chemical properties,and great efforts have been made in the past decades to find more effective synthetic methods.However,the established synthetic methods suffer from low efficiency and low selectivity because the mechanism of the B-H bond condensation reaction,critical for the synthesis of the polyhedral boranes,is not well understood.Here we report highly selective and efficient synthetic methods of the salts of the tetradecahydridoundecaborate(1-)(B_(11)H^(-)_(14)) and dodecahydrido-dodecaborates(2-)(B_(12)H_(12)^(2-)) anions by employing commercially available and inexpensive starting materials.Both theoretical and experimental investigations are carried out to elucidate the reaction mechanisms.We have found that the nature of the B-H bond condensation is the dihydrogen bonding interaction in which the positively charged hydrogens(bridged hydrogens) play a crucial role.The current study has not only led to more effective and selective synthetic methods for B_(11)H^(-)_(14) and B_(12)H_(12)^(2-) but also unveiled the nature of the B-H bond condensation and the general formation mechanisms of polyhedral boranes.This finding will facilitate the development of more effective synthetic methods for polyhedral boranes and spur their wide application.
基金supported by the Department of Energy,Office of Basic Energy Sciences,Chemical Sciences,Geosciences,and Biosciences Division under Grant DE-SC0018679.
文摘Valence-bound molecular anions with polar neutral cores(μ>2.5 D)can support highly diffuse dipole-bound states(DBSs)as electronically excited states just below the detachment threshold.Such weakly bound nonvalence excited states have little influence on the structure of the neutral core,and they usually have the same vibrational frequencies.DBSs can be systematically searched using photodetachment spectroscopy(PDS),which can yield the binding energies of the DBSs,the electron detachment threshold of the anion,and above-threshold vibrational levels of the DBSs(Feshbach resonances).We have shown that the combination of PDS and resonant photoelectron spectroscopy(rPES)at the Feshbach resonances is a powerful approach to obtain rich vibrational information for complex molecular radicals.A prerequisite for this technique is to produce vibrationally cold anions,made possible by a cryogenically controlled Paul trap.In this article,we report a PDS and rPES study of cold para-ethylphenolate anions(p-EP^(-)).The electron affinity of the p-EP radical is measured to be 17425±3 cm^(-1)(2.1604±0.0004 eV),and a DBS is found at 145 cm^(-1) below the detachment threshold of p-EP^(-).Thirty-four vibrational levels are observed for the DBS,including two bound levels and 32 Feshbach resonances.Frequencies for 17 vibrational modes of the p-EP radical are measured from the combination of PDS and rPES,including six symmetry-forbidden modes with A″symmetry.The current study confirms again the power of combining cryogenic ion cooling with PDS and highresolution rPES to obtain spectroscopic information on complex molecular radicals.
