A dual-switching spin crossover metal-organic framework(SCO-MOF)[Fe(TPB){Pt^(Ⅱ)(CN)_(4)}]·3iPrOH·4H_(2)O(TPB=1,2,4,5-tetra(pyridin-4-yl)benzene)is developed via the combination of redox-active framework and...A dual-switching spin crossover metal-organic framework(SCO-MOF)[Fe(TPB){Pt^(Ⅱ)(CN)_(4)}]·3iPrOH·4H_(2)O(TPB=1,2,4,5-tetra(pyridin-4-yl)benzene)is developed via the combination of redox-active framework and tunable guests.The reversible structural transformation between[Pt^(Ⅱ)(CN)_(4)]^(2-) and[Pt^(Ⅳ)Br_(2)(CN)_(4)]^(2-)moieties can be manipulated by redox post-synthetic modification(PSM),which results in the change of SCO behaviors from step-wise to one-step.The influences of the oxidative addition of bromides on the ligand field splitting of Fe side are further explored by density functional theory calculations.Besides,the modulation of hysteretic four-/three-step,one-step and four-step SCO behaviors can be achieved by tuning the composition of guest molecules.Therefore,the combination of electronic bistability,redox reaction and guest recognition in a homogeneous lattice provides a utility platform for designing multi-responsive molecule-based materials.展开更多
Spin-crossover(SCO)complexes with multiple spin states are promising candidates for high-order magnetic storage and multiple switches.Here,by employing the N,N'-4-dipyridyloxalamide(dpo)ligand,we synthesize two Ho...Spin-crossover(SCO)complexes with multiple spin states are promising candidates for high-order magnetic storage and multiple switches.Here,by employing the N,N'-4-dipyridyloxalamide(dpo)ligand,we synthesize two Hofmann-type metal-organic frameworks(MOFs)[Fe(dpo){Ag(CN)_(2)}_(2)]·3DMF(1)and[Fe(dpo){Ag(CN)_(2)}_(2)]·0.5MeCN·2DEF(2),which exhibit guest dependent four-step SCO behaviors with the sequences of LS→~LS_(2/3)HS_(1/3)→LS_(1/2)HS_(1/2)→~LS_(3/10)HS_(7/10)→HS and LS→~LS_(2/3)HS_(1/3)→LS_(1/2)HS_(1/2)→~LS_(1/4)HS_(3/4)→HS,respectively.Therefore,the incorporation of hydrogen-donating/hydrogen-accepting groups into the Hofmann-type MOFs may effectively explore the multi-step SCO materials by tuning hydrogen-bonding interactions.展开更多
基金supported by the National Key Research and Development Program of China(2018YFA0306001)the National Natural Science Foundation of China(22075323)+2 种基金the Pearl River Talent Plan of Guangdong(2017BT01C161)the Guangdong Special Fund for Science and Technology Innovation Strategy(pdjh2023b0019)the Guangdong University Student Innovation Training Project(202210386)。
文摘A dual-switching spin crossover metal-organic framework(SCO-MOF)[Fe(TPB){Pt^(Ⅱ)(CN)_(4)}]·3iPrOH·4H_(2)O(TPB=1,2,4,5-tetra(pyridin-4-yl)benzene)is developed via the combination of redox-active framework and tunable guests.The reversible structural transformation between[Pt^(Ⅱ)(CN)_(4)]^(2-) and[Pt^(Ⅳ)Br_(2)(CN)_(4)]^(2-)moieties can be manipulated by redox post-synthetic modification(PSM),which results in the change of SCO behaviors from step-wise to one-step.The influences of the oxidative addition of bromides on the ligand field splitting of Fe side are further explored by density functional theory calculations.Besides,the modulation of hysteretic four-/three-step,one-step and four-step SCO behaviors can be achieved by tuning the composition of guest molecules.Therefore,the combination of electronic bistability,redox reaction and guest recognition in a homogeneous lattice provides a utility platform for designing multi-responsive molecule-based materials.
基金supported by the National Key Research and Development Program of China(No.2018YFA0306001)the National Natural Science Foundation of China(Nos.21950410521,21771200and 21773316)the Pearl River Talent Plan of Guangdong(No.2017BT01C161)。
文摘Spin-crossover(SCO)complexes with multiple spin states are promising candidates for high-order magnetic storage and multiple switches.Here,by employing the N,N'-4-dipyridyloxalamide(dpo)ligand,we synthesize two Hofmann-type metal-organic frameworks(MOFs)[Fe(dpo){Ag(CN)_(2)}_(2)]·3DMF(1)and[Fe(dpo){Ag(CN)_(2)}_(2)]·0.5MeCN·2DEF(2),which exhibit guest dependent four-step SCO behaviors with the sequences of LS→~LS_(2/3)HS_(1/3)→LS_(1/2)HS_(1/2)→~LS_(3/10)HS_(7/10)→HS and LS→~LS_(2/3)HS_(1/3)→LS_(1/2)HS_(1/2)→~LS_(1/4)HS_(3/4)→HS,respectively.Therefore,the incorporation of hydrogen-donating/hydrogen-accepting groups into the Hofmann-type MOFs may effectively explore the multi-step SCO materials by tuning hydrogen-bonding interactions.
