Two-dimensional transition metal porphyrinoid materials(2DTMPoidMats),due to their unique electronic structure and tunable metal active sites,have the potential to enhance interactions with nitrogen molecules and prom...Two-dimensional transition metal porphyrinoid materials(2DTMPoidMats),due to their unique electronic structure and tunable metal active sites,have the potential to enhance interactions with nitrogen molecules and promote the protonation process,making them promising electrochemical nitrogen reduction reaction(eNRR)electrocatalysts.Experimentally screening a large number of catalysts for eNRR catalytic performance would consume considerable time and economic resources.First-principles calculations and machine learning(ML)algorithms could greatly improve the efficiency of catalyst screening.Using this approach,we selected 86 candidates capable of catalyzing eNRR from 1290 types of 2DTMPoidMats,and verified the results with density functional theory(DFT)computations.Analysis of the full reaction pathway shows that MoPp-meso-F-β-Py,MoPp-β-Cl-meso-Diyne,MoPp-meso-Ethinyl,and WPp-β-Pz exhibit the best catalytic performance with the onset potential of-0.22,-0.19,-0.23,and-0.35 V,respectively.This work provides valuable insights into efficient design and screening of eNRR catalysts and promotes the application of ML algorithmic models in the field of catalysis.展开更多
Novel expanded porphyrinoids with advanced structure features(such as multiple-inner-ring-fusion)have a wide range of benefits(such as multi-metal coordination and facile tunable aromaticity)not offered by their norma...Novel expanded porphyrinoids with advanced structure features(such as multiple-inner-ring-fusion)have a wide range of benefits(such as multi-metal coordination and facile tunable aromaticity)not offered by their normal porphyrin analogues,and have found wide applications as sensors,fluorescent probes,novel ligands and functionalized NIR organic dyes in various research fields.However,the structures of these expanded porphyrinoids are scarce due to their limited synthetic accessibility.Herein,we summarized the lately reported efficient synthesis of novel expanded porphyrinoids with multipleinner-ring-fusion(up to six-inner-ring-fusion)and smaragdyrins with tunable aromaticity.Their synthesis is either based on an oxidative ring cyclization on linear/macrocyclic oligopyrroles containing N-confused pyrrole unit(s)or a straightforward double SNAr reaction on readily available 3,5-dibromoBODIPY,respectively.展开更多
Buchwald-Hartwig amination of 5,15-dibromo and 5,10-dibromo Ni(Ⅱ)porphyrins with 5-amino Ni(Ⅱ)porphyrin gave linear and bent trimers 4Ni and 5Ni with a central quinodiimine-type Ni(Ⅱ)porphyrinoid.The structures of ...Buchwald-Hartwig amination of 5,15-dibromo and 5,10-dibromo Ni(Ⅱ)porphyrins with 5-amino Ni(Ⅱ)porphyrin gave linear and bent trimers 4Ni and 5Ni with a central quinodiimine-type Ni(Ⅱ)porphyrinoid.The structures of 4Ni and 5Ni have been confirmed by X-ray diffraction analysis in both cases.The formation of unusual products 4Ni and 5Ni has been ascribed to facile oxidation of 5,15-and 5,10-amino Ni(Ⅱ)porphyrin unit.Reduction of 4Ni and 5Ni under proper conditions gave NH-bridged Ni(Ⅱ)porphyrin trimers 4Ni-2H and 5Ni-2H in high yields.Trimers 4Ni and 5Ni exhibit the lowest energy band as compared with 4Ni-2H and 5Ni-2H.Especially the bent trimer 5Ni exhibits a broad absorption tail beyond 1400 nm.展开更多
Preparing free-base porphyrinoid radicals that can function as coordination ligands is a challenging task.Here we report the synthesis of a stable,free-base benzocorrole(BC)radical containing only two inner NH protons...Preparing free-base porphyrinoid radicals that can function as coordination ligands is a challenging task.Here we report the synthesis of a stable,free-base benzocorrole(BC)radical containing only two inner NH protons via a retro-Diels-Alder conversion.The radical character of BC was fully supported by crystallographic analysis,spectroscopic evidence,and theoretical calculations.This neutral radical ligand allowed easy insertion of Zn(Ⅱ),Ga(Ⅲ),and Pd(Ⅱ)ions to produce radical complexes.All these radicals exhibited luminescence-on responses under weak reducing atmosphere,corresponding to the conversion to their aromatic anions.The red fluorescence was observed for BC and its Zn(Ⅱ)and Ga(Ⅲ)complexes,and the near-infrared phosphorescence(>900 nm)was detected for Pd(Ⅱ)complex at room temperature.Furthermore,Ga(Ⅲ)corrole exhibited a variation in fluorescence in response to axial coordination.Our findings provide a promising radical platform for coordination and developing novel functional materials with switchable spin and emission.展开更多
Materials with facilely tunable spin configurations based on metal-radical coordination systems have potential applications for electronics and spintronics.Here,we report the ground state conversion of copper corrole ...Materials with facilely tunable spin configurations based on metal-radical coordination systems have potential applications for electronics and spintronics.Here,we report the ground state conversion of copper corrole radicals from singlet to triplet via the extension of theπ-conjugation system by benzo-fusion at theβ-position of corrole ligand.NMR spectroscopy,SQUID measurements and computational studies all support the ferromagnetic coupling between the Cu(II)center and corroleπ-radical of benzo-fused copper corrole 2-Cu,which is in sharp contrast with the antiferromagnetic coupling in regular non-extended copper corroles.The triplet 2-Cu is highly stable in air,and X-ray diffraction analysis revealed its unique highly planar corrole macrocycle.This work offers a promising strategy for creating high-spin systems in non-innocent metallocorroles.展开更多
Porphyrin-functionalized reduced graphene oxide (RGO-TPP) was prepared by 1,3-dipolar cycloaddition reaction and characterized by Fourier transform infrared spectroscopy, Raman, ultraviolet/visible absorption, fluores...Porphyrin-functionalized reduced graphene oxide (RGO-TPP) was prepared by 1,3-dipolar cycloaddition reaction and characterized by Fourier transform infrared spectroscopy, Raman, ultraviolet/visible absorption, fluorescence, and transmission electron microscopy. At the same level of linear transmittance, RGO-TPP exhibited more enhanced optical nonlinearities than RGO and the pristineporphyrin, implying a remarkable accumulation effect as a result of the covalent link between RGO and porphyrin. The role of energy/electron transfer in the optical nonlinearities of RGO-TPP was investigated by fluorescence and Raman spectroscopy. All the results displayed that RGO can be covalently functionalized with porphyrins by the proposed approach.展开更多
Designing stable molecules with efficient near-infrared(NIR) photothermal/photoacoustic performances is important for biological and environmental applications.In this article,we inserted paramagnetic Cu(Ⅱ) into tetr...Designing stable molecules with efficient near-infrared(NIR) photothermal/photoacoustic performances is important for biological and environmental applications.In this article,we inserted paramagnetic Cu(Ⅱ) into tetraanthraporphyrin to generate a highly photostable molecule,Cu ANP,which demonstrated a sharp,intense Q band in the NIR region above 800 nm.Unlike its diamagnetic Zn(Ⅱ)-coordinated analog Zn ANP that degraded rapidly under ambient light,Cu ANP has a low-lying singly unoccupied d orbital that quenched radioactive emission and reactive oxygen generation effectively,resulting in fast photothermal response,excellent photothermal conversion capacity and heat endurance under long-term laser irradiation in an organic solvent,in water after encapsulation as a nanocomposite,and in the solid state.Cu ANP also exhibited an intense NIR photoacoustic response and was reversibly redox-active,displaying a broad band spreading to the NIR-Ⅱ window(700–1,300 nm) in the dicationic state.This paramagnetic metal incorporation strategy can enhance the performance of photolabile NIR absorbing molecules for a variety of photothermal/photoacoustic applications.展开更多
Metallocorrole macrocycles that represent a burgeoning class of attractive metal-complexes from the porphyrinoid family,have attracted great interest in recent years owing to their unique structure and excellent perfo...Metallocorrole macrocycles that represent a burgeoning class of attractive metal-complexes from the porphyrinoid family,have attracted great interest in recent years owing to their unique structure and excellent performance revealed in many fields,yet further functionalization through incorporating these motifs into porous nanomaterials employing the bottom-up approach is still scarce and remains synthetically challenging.Here,we report the targeted synthesis of porous organic polymers(POPs)constructed from custom-designed Mn and Fe-corrole complex building units,respectively denoted as CorPOP-1(Mn)and CorPOP-1(FeCl).Specifically,the robust CorPOP-1(Mn)bearing Mn-corrole active centers displays superior heterogeneous catalytic activity toward solvent-free cycloaddition of carbon dioxide(CO_(2))with epoxides to form cyclic carbonates under mild reaction conditions as compared with the homogeneous counterpart.CorPOP-1(Mn)can be easily recycled and does not show significant loss of reactivity after seven successive cycles.This work highlights the potential of metallocorrole-based porous solid catalysts for targeting CO_(2) transformations,and would provide a guide for the task-specific development of more corrole-based multifunctional materials for extended applications.展开更多
Over the past few years,the development of nonfullerene acceptors(NFAs)has become a prominent focus in both organic and perovskite solar cell(OSCs and PSCs,respectively)research fields.In this context,porphyrinoids,co...Over the past few years,the development of nonfullerene acceptors(NFAs)has become a prominent focus in both organic and perovskite solar cell(OSCs and PSCs,respectively)research fields.In this context,porphyrinoids,compounds structurally related to porphyrins,have emerged as promising solar cell candidates.In contrast to the widely used fullerene acceptors,porphyrinoids exhibit strong,broad absorption properties across the UV–vis/NIR spectrum,which can be easily tuned through chemical modifications.Furthermore,they can be prepared and derivatized using cost-effective and straightforward methodologies,allowing for convenient adjustments in thin-film morphology,processability,supramolecular organization,and energy levels.Additionally,these compounds offer higher thermal and photochemical stability,resulting in longer device lifetimes compared to their fullerene-based counterparts.In this review,we outline the utilization of porphyrinoids as NFAs in OSCs and PSCs,discussing essential aspects such as design guidelines,molecular properties,and device configuration.Our goal is to inspire and further promote the development of n-type porphyrinoids,which have not yet fully unleashed their potential.展开更多
Four awl-substituted tripyrrinone copper（II） complexes were synthesized and characterized as to their electro- chemical and spectroelectrochemical properties. The examined compounds are represented as （YPh）3TPO2Cu...Four awl-substituted tripyrrinone copper（II） complexes were synthesized and characterized as to their electro- chemical and spectroelectrochemical properties. The examined compounds are represented as （YPh）3TPO2Cu, where TPO2 is a dianion of the tripyrrinone and Y is a CH3O, CH3, H or CI substituent on the para-position of each phenyl ring of the compound. The neutral compounds are ESR active and show a typical d9 Cu（II） signal in frozen CH2C12 solution. Each Cu（II） compound undergoes three reductions between -0.61 and -1.90 V and two oxidations between 1.00 and 1.24 V in CH2Cl2 containing 0.1 mol/L tetra-n-butylammonium perchlorate. The potentials for oxidation are similar to those of copper tetraarylporphyrins but the reduction potentials are positively shifted as compared to the corresponding tetraarylporphyrins. Thus, the potential difference between the first one-electron oxidation and first one-electron reduction （the HOMO-LUMO gap） of （YPh）3TPO2Cu, which ranges from 1.68 to 1.75 V, is similar to that of copper corroles （1.73-1.85 V）, but smaller than the separation of 2.30-2.37 V for the copper tetraarylporphyrins under the same solution conditions.展开更多
Suitable conformations and proper alignment of complex natural macrocycles are essential for achieving their unique properties.However,such artificial macrocycle prototypes are still limited due to synthetic difficult...Suitable conformations and proper alignment of complex natural macrocycles are essential for achieving their unique properties.However,such artificial macrocycle prototypes are still limited due to synthetic difficulties.In this respect,directly linked porphyrin analog dimers display tunable conformations and intriguing properties,and thus,they may be employed as a class of promising platforms.Herein,we report that one-pot oxidative dimerization of thiahydrosapphyrin 1 yields dimers,2anti and 2syn,comprising a transoid-oriented plate-like bipyrrolo[1,2-a]indolylidene.The thiophene-containing tetrapyrrole arching subunits in 2 lie at the opposite(anti)and same(syn)sides of the plate,respectively.Meanwhile,multiply fused cisoid-orientated dimer 3 was also obtained;a polycyclic pyrrolo-bridged bipyrroloindole derivative tethered with fullyπ-conjugated bridges was formed.Notably,the anti-dimer 2anti underwent subsequent oxidative fusion to furnish a further-fused[6.5.5.7.5.5.5.6]-octacyclic compound 4anti.In contrast,the syn-orientated 2syn could not be further fused due to the long distance between the potential reaction sites.This study provides a unique approach to the fused dimeric porphyrin analogs for potential near-infrared optical materials by a simple oxidation reaction.It also reveals the importance of conformation-modulated reactivity for constructing complex porphyrin arrays.展开更多
基金support from the National Natural Science Foundation of China(22073033,21873032,21673087,21903032)startup fund(2006013118 and 3004013105)from Huazhong University of Science and Technology,the Fundamental Research Funds for the Central Universities(2019kfyRCPY116)+1 种基金the Innovation and Talent Recruitment Base of New Energy Chemistry and Device(B21003)supported by the public computing service platform provided by the Network and Computing Center of HUST.
文摘Two-dimensional transition metal porphyrinoid materials(2DTMPoidMats),due to their unique electronic structure and tunable metal active sites,have the potential to enhance interactions with nitrogen molecules and promote the protonation process,making them promising electrochemical nitrogen reduction reaction(eNRR)electrocatalysts.Experimentally screening a large number of catalysts for eNRR catalytic performance would consume considerable time and economic resources.First-principles calculations and machine learning(ML)algorithms could greatly improve the efficiency of catalyst screening.Using this approach,we selected 86 candidates capable of catalyzing eNRR from 1290 types of 2DTMPoidMats,and verified the results with density functional theory(DFT)computations.Analysis of the full reaction pathway shows that MoPp-meso-F-β-Py,MoPp-β-Cl-meso-Diyne,MoPp-meso-Ethinyl,and WPp-β-Pz exhibit the best catalytic performance with the onset potential of-0.22,-0.19,-0.23,and-0.35 V,respectively.This work provides valuable insights into efficient design and screening of eNRR catalysts and promotes the application of ML algorithmic models in the field of catalysis.
基金the National Nature Science Foundation of China(Nos.21672006,21672007 and 21871006)for supporting this work
文摘Novel expanded porphyrinoids with advanced structure features(such as multiple-inner-ring-fusion)have a wide range of benefits(such as multi-metal coordination and facile tunable aromaticity)not offered by their normal porphyrin analogues,and have found wide applications as sensors,fluorescent probes,novel ligands and functionalized NIR organic dyes in various research fields.However,the structures of these expanded porphyrinoids are scarce due to their limited synthetic accessibility.Herein,we summarized the lately reported efficient synthesis of novel expanded porphyrinoids with multipleinner-ring-fusion(up to six-inner-ring-fusion)and smaragdyrins with tunable aromaticity.Their synthesis is either based on an oxidative ring cyclization on linear/macrocyclic oligopyrroles containing N-confused pyrrole unit(s)or a straightforward double SNAr reaction on readily available 3,5-dibromoBODIPY,respectively.
基金supported by the National Natural Science Foundation of China(Nos.21772036,22071052,21602058,21702057)the Science and Technology Planning Project of Hunan Province(No.2018TP1017)+1 种基金the Scientific Research Fund of Hunan Provincial Education Department(No.19A331)Hunan Provincial Innovation Foundation for Postgraduate(No.CX20210473)。
文摘Buchwald-Hartwig amination of 5,15-dibromo and 5,10-dibromo Ni(Ⅱ)porphyrins with 5-amino Ni(Ⅱ)porphyrin gave linear and bent trimers 4Ni and 5Ni with a central quinodiimine-type Ni(Ⅱ)porphyrinoid.The structures of 4Ni and 5Ni have been confirmed by X-ray diffraction analysis in both cases.The formation of unusual products 4Ni and 5Ni has been ascribed to facile oxidation of 5,15-and 5,10-amino Ni(Ⅱ)porphyrin unit.Reduction of 4Ni and 5Ni under proper conditions gave NH-bridged Ni(Ⅱ)porphyrin trimers 4Ni-2H and 5Ni-2H in high yields.Trimers 4Ni and 5Ni exhibit the lowest energy band as compared with 4Ni-2H and 5Ni-2H.Especially the bent trimer 5Ni exhibits a broad absorption tail beyond 1400 nm.
基金supported by the National Natural Science Foundation of China(Nos.22271140,22071103,and 22371118)。
文摘Preparing free-base porphyrinoid radicals that can function as coordination ligands is a challenging task.Here we report the synthesis of a stable,free-base benzocorrole(BC)radical containing only two inner NH protons via a retro-Diels-Alder conversion.The radical character of BC was fully supported by crystallographic analysis,spectroscopic evidence,and theoretical calculations.This neutral radical ligand allowed easy insertion of Zn(Ⅱ),Ga(Ⅲ),and Pd(Ⅱ)ions to produce radical complexes.All these radicals exhibited luminescence-on responses under weak reducing atmosphere,corresponding to the conversion to their aromatic anions.The red fluorescence was observed for BC and its Zn(Ⅱ)and Ga(Ⅲ)complexes,and the near-infrared phosphorescence(>900 nm)was detected for Pd(Ⅱ)complex at room temperature.Furthermore,Ga(Ⅲ)corrole exhibited a variation in fluorescence in response to axial coordination.Our findings provide a promising radical platform for coordination and developing novel functional materials with switchable spin and emission.
基金supported by the National Natural Science Foundation of China(Nos.22071103,22001119 and 21911540069)the Program A for Outstanding PhD Candidate of Nanjing University(No.202201A006).
文摘Materials with facilely tunable spin configurations based on metal-radical coordination systems have potential applications for electronics and spintronics.Here,we report the ground state conversion of copper corrole radicals from singlet to triplet via the extension of theπ-conjugation system by benzo-fusion at theβ-position of corrole ligand.NMR spectroscopy,SQUID measurements and computational studies all support the ferromagnetic coupling between the Cu(II)center and corroleπ-radical of benzo-fused copper corrole 2-Cu,which is in sharp contrast with the antiferromagnetic coupling in regular non-extended copper corroles.The triplet 2-Cu is highly stable in air,and X-ray diffraction analysis revealed its unique highly planar corrole macrocycle.This work offers a promising strategy for creating high-spin systems in non-innocent metallocorroles.
文摘Porphyrin-functionalized reduced graphene oxide (RGO-TPP) was prepared by 1,3-dipolar cycloaddition reaction and characterized by Fourier transform infrared spectroscopy, Raman, ultraviolet/visible absorption, fluorescence, and transmission electron microscopy. At the same level of linear transmittance, RGO-TPP exhibited more enhanced optical nonlinearities than RGO and the pristineporphyrin, implying a remarkable accumulation effect as a result of the covalent link between RGO and porphyrin. The role of energy/electron transfer in the optical nonlinearities of RGO-TPP was investigated by fluorescence and Raman spectroscopy. All the results displayed that RGO can be covalently functionalized with porphyrins by the proposed approach.
基金supported by the National Natural Science Foundation of China(22071103,21911540069 to Z.S.and22001119 to F.W.)。
文摘Designing stable molecules with efficient near-infrared(NIR) photothermal/photoacoustic performances is important for biological and environmental applications.In this article,we inserted paramagnetic Cu(Ⅱ) into tetraanthraporphyrin to generate a highly photostable molecule,Cu ANP,which demonstrated a sharp,intense Q band in the NIR region above 800 nm.Unlike its diamagnetic Zn(Ⅱ)-coordinated analog Zn ANP that degraded rapidly under ambient light,Cu ANP has a low-lying singly unoccupied d orbital that quenched radioactive emission and reactive oxygen generation effectively,resulting in fast photothermal response,excellent photothermal conversion capacity and heat endurance under long-term laser irradiation in an organic solvent,in water after encapsulation as a nanocomposite,and in the solid state.Cu ANP also exhibited an intense NIR photoacoustic response and was reversibly redox-active,displaying a broad band spreading to the NIR-Ⅱ window(700–1,300 nm) in the dicationic state.This paramagnetic metal incorporation strategy can enhance the performance of photolabile NIR absorbing molecules for a variety of photothermal/photoacoustic applications.
基金supported by the National Natural Science foundation of China(NSFC)(22078241)China Scholarship Council(CSC)(No.201706250095).
文摘Metallocorrole macrocycles that represent a burgeoning class of attractive metal-complexes from the porphyrinoid family,have attracted great interest in recent years owing to their unique structure and excellent performance revealed in many fields,yet further functionalization through incorporating these motifs into porous nanomaterials employing the bottom-up approach is still scarce and remains synthetically challenging.Here,we report the targeted synthesis of porous organic polymers(POPs)constructed from custom-designed Mn and Fe-corrole complex building units,respectively denoted as CorPOP-1(Mn)and CorPOP-1(FeCl).Specifically,the robust CorPOP-1(Mn)bearing Mn-corrole active centers displays superior heterogeneous catalytic activity toward solvent-free cycloaddition of carbon dioxide(CO_(2))with epoxides to form cyclic carbonates under mild reaction conditions as compared with the homogeneous counterpart.CorPOP-1(Mn)can be easily recycled and does not show significant loss of reactivity after seven successive cycles.This work highlights the potential of metallocorrole-based porous solid catalysts for targeting CO_(2) transformations,and would provide a guide for the task-specific development of more corrole-based multifunctional materials for extended applications.
基金T.T.acknowledges financial support from the Spanish MCIN/AEI/10.13039/501100011033(PID2020-116490GBI00,TED2021-131255B-C43)the Comunidad de Madrid and the Spanish State through the Recovery,Transformation and Resilience Plan[“Materiales Disruptivos Bidimensionales(2D)”(MAD2D-CM)(UAM1)-MRR Materiales Avanzados]+2 种基金the European Union through the Next Generation EU funds.Instituto madrileno de estudios avanzados Nanociencia acknowledges support from the“Severo Ochoa”Programme for Centres of Excellence in R&D(Ministerio de asuntos economicos y transformacion digital,Grant SEV2016-0686)T.T.also acknowledges the Alexander von Humboldt Foundation(Germany)for the A.v.Humboldt-J.C.Mutis Research Award 2023(Ref 3.3-1231125-ESP-GSA)J.L.acknowledgesMinisterio de Eduacion,Cultura y Deporte(MECD),Spain,for an F.P.U.Fellowship.
文摘Over the past few years,the development of nonfullerene acceptors(NFAs)has become a prominent focus in both organic and perovskite solar cell(OSCs and PSCs,respectively)research fields.In this context,porphyrinoids,compounds structurally related to porphyrins,have emerged as promising solar cell candidates.In contrast to the widely used fullerene acceptors,porphyrinoids exhibit strong,broad absorption properties across the UV–vis/NIR spectrum,which can be easily tuned through chemical modifications.Furthermore,they can be prepared and derivatized using cost-effective and straightforward methodologies,allowing for convenient adjustments in thin-film morphology,processability,supramolecular organization,and energy levels.Additionally,these compounds offer higher thermal and photochemical stability,resulting in longer device lifetimes compared to their fullerene-based counterparts.In this review,we outline the utilization of porphyrinoids as NFAs in OSCs and PSCs,discussing essential aspects such as design guidelines,molecular properties,and device configuration.Our goal is to inspire and further promote the development of n-type porphyrinoids,which have not yet fully unleashed their potential.
基金Support from the National Natural Science Foundation of China （Nos. 21501070, 21071067）, Jiangsu University Foundation （Nos. 05JDG051, 15JDG131） and the Robert A. Welch Foundation （K.M.K., E-680） are gratefully acknowledged.
文摘Four awl-substituted tripyrrinone copper（II） complexes were synthesized and characterized as to their electro- chemical and spectroelectrochemical properties. The examined compounds are represented as （YPh）3TPO2Cu, where TPO2 is a dianion of the tripyrrinone and Y is a CH3O, CH3, H or CI substituent on the para-position of each phenyl ring of the compound. The neutral compounds are ESR active and show a typical d9 Cu（II） signal in frozen CH2C12 solution. Each Cu（II） compound undergoes three reductions between -0.61 and -1.90 V and two oxidations between 1.00 and 1.24 V in CH2Cl2 containing 0.1 mol/L tetra-n-butylammonium perchlorate. The potentials for oxidation are similar to those of copper tetraarylporphyrins but the reduction potentials are positively shifted as compared to the corresponding tetraarylporphyrins. Thus, the potential difference between the first one-electron oxidation and first one-electron reduction （the HOMO-LUMO gap） of （YPh）3TPO2Cu, which ranges from 1.68 to 1.75 V, is similar to that of copper corroles （1.73-1.85 V）, but smaller than the separation of 2.30-2.37 V for the copper tetraarylporphyrins under the same solution conditions.
基金The authors thank the Research Center of Analysis and Test of East China University of Science and Technology for compound characterization.
文摘Suitable conformations and proper alignment of complex natural macrocycles are essential for achieving their unique properties.However,such artificial macrocycle prototypes are still limited due to synthetic difficulties.In this respect,directly linked porphyrin analog dimers display tunable conformations and intriguing properties,and thus,they may be employed as a class of promising platforms.Herein,we report that one-pot oxidative dimerization of thiahydrosapphyrin 1 yields dimers,2anti and 2syn,comprising a transoid-oriented plate-like bipyrrolo[1,2-a]indolylidene.The thiophene-containing tetrapyrrole arching subunits in 2 lie at the opposite(anti)and same(syn)sides of the plate,respectively.Meanwhile,multiply fused cisoid-orientated dimer 3 was also obtained;a polycyclic pyrrolo-bridged bipyrroloindole derivative tethered with fullyπ-conjugated bridges was formed.Notably,the anti-dimer 2anti underwent subsequent oxidative fusion to furnish a further-fused[6.5.5.7.5.5.5.6]-octacyclic compound 4anti.In contrast,the syn-orientated 2syn could not be further fused due to the long distance between the potential reaction sites.This study provides a unique approach to the fused dimeric porphyrin analogs for potential near-infrared optical materials by a simple oxidation reaction.It also reveals the importance of conformation-modulated reactivity for constructing complex porphyrin arrays.
