As a new class of porous solid materials with structural variability,notable porosity,and good dispersibility,metal-organic cages(MOCs)have shown great promise as filler components for separation membranes.Research in...As a new class of porous solid materials with structural variability,notable porosity,and good dispersibility,metal-organic cages(MOCs)have shown great promise as filler components for separation membranes.Research into MOC-based membranes has blossomed over the last decade because of their high performance in separation,desalination,and artificial channel.In this review,we summarize current membranes based on MOCs including mixed matrix membranes,cross-linked membranes,composite membranes,bilayer lipid membranes,and liquid membranes,and provide a brief overview of their applications.The challenges and opportunities in future developments are also discussed.展开更多
The search for new methodologies to tune and control the enantioselectivities of molecular catalysts is of great importance in the field of asymmetric catalysis.Here,we have illustrated that chiral molecular catalysts...The search for new methodologies to tune and control the enantioselectivities of molecular catalysts is of great importance in the field of asymmetric catalysis.Here,we have illustrated that chiral molecular catalysts can be boosted from very low enantioselectivity to high enantioselectivity when installed in supramolecular metal-organic cages.By deliberately designing two optically active 1,1′-spirobiindane-7,7′-diol(SPINOL)-based dipyridine linkers,we synthesized two chiral Pd_(3)L_(6) cages featuring chiral dihydroxyl or dimethoxymethyl auxiliaries in the nanosized cavities.After treatment with metal ions,the cage featuring dihydroxyl groups could serve as efficient catalysts for asymmetric conjugate addition of styrylboronic acids toα,β-enones to produce γ,δ-unsaturated ketone and the asymmetric addition of diethylzinc to aldehydes to afford secondary alcohols.While the molecular SPINOL display very low enantioselectivity,restriction of its freedom in the cages led to 91−99.6% and 80−99.9% enantiomeric excess(ee)of products,respectively,which were increased by up to 35% and 78% ee,compared with the molecular control.Thus,our present work paves a way of utilizing supramolecular porous assemblies to manipulate the enantioselectivities of molecular catalysts.展开更多
基金supported by the National Key R&D Program of China(2022YFA1503302,2021YFA1200402,2021YFA1200302,2021YFA1501501)the National Natural Science Foundation of China(22225111)+1 种基金the Key Project of Basic Research of Shanghai(21JC1401700,22JC1402000)Shenzhen Science and Technology Program(CJGJZD20210408091800002)。
文摘As a new class of porous solid materials with structural variability,notable porosity,and good dispersibility,metal-organic cages(MOCs)have shown great promise as filler components for separation membranes.Research into MOC-based membranes has blossomed over the last decade because of their high performance in separation,desalination,and artificial channel.In this review,we summarize current membranes based on MOCs including mixed matrix membranes,cross-linked membranes,composite membranes,bilayer lipid membranes,and liquid membranes,and provide a brief overview of their applications.The challenges and opportunities in future developments are also discussed.
基金supported by the National Natural Science Foundation of China(grant nos.91956124,21875136,21620102001,and 91856204)the National Key Basic Research Program of China(grant no.2016YFA0203400)+1 种基金Key Project of Basic Research of Shanghai(grant nos.19JC1412600 and 18JC1413200)Shanghai Rising-Star Program(grant no.19QA1404300).
文摘The search for new methodologies to tune and control the enantioselectivities of molecular catalysts is of great importance in the field of asymmetric catalysis.Here,we have illustrated that chiral molecular catalysts can be boosted from very low enantioselectivity to high enantioselectivity when installed in supramolecular metal-organic cages.By deliberately designing two optically active 1,1′-spirobiindane-7,7′-diol(SPINOL)-based dipyridine linkers,we synthesized two chiral Pd_(3)L_(6) cages featuring chiral dihydroxyl or dimethoxymethyl auxiliaries in the nanosized cavities.After treatment with metal ions,the cage featuring dihydroxyl groups could serve as efficient catalysts for asymmetric conjugate addition of styrylboronic acids toα,β-enones to produce γ,δ-unsaturated ketone and the asymmetric addition of diethylzinc to aldehydes to afford secondary alcohols.While the molecular SPINOL display very low enantioselectivity,restriction of its freedom in the cages led to 91−99.6% and 80−99.9% enantiomeric excess(ee)of products,respectively,which were increased by up to 35% and 78% ee,compared with the molecular control.Thus,our present work paves a way of utilizing supramolecular porous assemblies to manipulate the enantioselectivities of molecular catalysts.
