Jian-Yu Zheng

•Three novel organic dyes with fused tetracyclic donor were designed for DSSCs.•The nonplanar conformation of the dyes can impede dye aggregation.•The effect of π-linkers on the photovoltaic properties of the dyes was evaluated.•An attractive PCE up to 7.54% has been achieved.Novel metal-free organic dyes based on polycyclic aromatic donor, pyrrolo[3,2,1-kl]phenothiazine, have been synthesized and applied in dye-sensitized solar cells. Combined with cyanoacrylic acid as the acceptor/anchoring group and simple π-spacers such as thiophene (JY40), furan (JY41), and terthiophene (JY42) as the conjugated linker, these dyes show good power conversion efficiency (PCE). The photophysical, electrochemical and photovoltaic properties, as well as theoretical calculations of these dyes were fully investigated. An attractive PCE up to 7.54%, with a short-circuit photocurrent density (Jsc) of 17.76 mA cm−2, an open-circuit photovoltage (Voc) of 726 mV, and a fill factor (FF) of 0.58 has been achieved by the JY42-based cell under standard AM 1.5 G irradiation in conjunction with an iodine electrolyte.Download high-res image (180KB)Download full-size image

Phenothiazine-functionalized push–pull Zn porphyrin photosensitizers for efficient dye-sensitized solar cells

Co-reporter:Xing Qian, Lin Lu, Yi-Zhou Zhu, Huan-Huan Gao and Jian-Yu Zheng

RSC Advances 2016 vol. 6(Issue 11) pp:9057-9065

Publication Date(Web):15 Jan 2016

DOI:10.1039/C5RA26754D

A series of zinc porphyrin dyes (JY24–27) featured phenothiazine moieties have been synthesized and applied as photosensitizers in dye-sensitized solar cells. The phenothiazine donors were directly attached to the meso-position of porphyrins, and different π-linkers (benzene, thiophene and ethynyl benzene) and acceptor groups (carboxylic acid and cyanoacrylic acid) were applied to tune the photoelectric properties of these push–pull porphyrin dyes. The photophysical, electrochemical and theoretical studies revealed that the synthesized porphyrin dyes were all capable of being used as photosensitizer. The dye JY27 with an extended conjugation by introducing ethynyl group exhibited a broader absorption region and more significantly improved IPCE values between 550 and 750 nm than the other three dyes, which ensured a good light-harvesting ability and a high short-circuit current density of 15.3 mA cm−2. Finally, JY27-based cell achieved a high efficiency of 6.25% under standard simulated irradiation.

A meso–meso directly linked porphyrin dimer-based double D–π–A sensitizer for efficient dye-sensitized solar cells

Co-reporter:Tao Zhang, Xing Qian, Peng-Fei Zhang, Yi-Zhou Zhu and Jian-Yu Zheng

Chemical Communications 2015 vol. 51(Issue 18) pp:3782-3785

Publication Date(Web):27 Jan 2015

DOI:10.1039/C4CC09640A

A novel double D–π–A branched dye (JY07) was synthesized and applied as a sensitizer for DSSCs. JY07 exhibited broader and stronger light absorption capability than the single D–π–A dye (JY06). In the meantime, the orthogonal conformation of JY07 was found to be favorable for impeding intermolecular aggregation. Consequently, a power conversion efficiency of 5.33% was achieved under AM 1.5G conditions.

Benzo[a]carbazole-Based Donor−π–Acceptor Type Organic Dyes for Highly Efficient Dye-Sensitized Solar Cells

Co-reporter:Xing Qian, Yi-Zhou Zhu, Wen-Ying Chang, Jian Song, Bin Pan, Lin Lu, Huan-Huan Gao, and Jian-Yu Zheng

ACS Applied Materials & Interfaces 2015 Volume 7(Issue 17) pp:9015

Publication Date(Web):April 15, 2015

DOI:10.1021/am508400a

A novel class of metal-free organic dyes based on benzo[a]carbazole have been designed, synthesized, and used in dye-sensitized solar cells for the first time. These types of dyes consisted of a cyanoacrylic acid moiety as the electron acceptor/anchoring group and different electron-rich spacers such as thiophene (JY21), furan (JY22), and oligothiophene (JY23) as the π-linkers. The photophysical, electrochemical, and photovoltaic properties, as well as theoretical calculations of these dyes were investigated. The photovoltaic performances of these dyes were found to be highly relevant to the π-conjugated linkers. In particular, dye JY23 exhibited a broad IPCE response with a photocurrent signal up to about 740 nm covering the most region of the UV–visible light. A DSSC based on JY23 showed the best photovoltaic performance with a Jsc of 14.8 mA cm–2, a Voc of 744 mV, and a FF of 0.68, achieving a power conversion efficiency of 7.54% under standard AM 1.5 G irradiation.Keywords: benzo[a]carbazole; conjugated linkers; dye-sensitized solar cells; intramolecular charge transfer; organic dyes;

Tetraindole-based saddle-shaped organic dyes for efficient dye-sensitized solar cells

Co-reporter:Xing Qian, Huan-Huan Gao, Yi-Zhou Zhu, Bin Pan, Jian-Yu Zheng

Dyes and Pigments 2015 Volume 121() pp:152-158

Publication Date(Web):October 2015

DOI:10.1016/j.dyepig.2015.05.015

•Tetraindole-based organic dyes have been synthesized for the first time.•The saddle-shaped structure is favourable for suppressing the dye aggregation.•The dye with a bithiophene as the π-bridge exhibited better performances.•An efficiency up to 6.46% has been achieved with a high Voc of 762 mV.Two new metal-free organic dyes which consist of a saddle-shaped tetraindole donor, a cyanoacrylic acid acceptor/anchoring group and a thiophene or bithiophene π-bridge have been successfully designed and synthesized for dye-sensitized solar cells. The two dyes showed good photoelectric properties, and the saddle-shaped structure of the tetraindole unit was found to be favorable for preventing intermolecular aggregation and enhancing the photovoltage. The two tetraindole-based dyes exhibited good photovoltaic performances in solar cells. An efficiency up to 6.46% with a high open-circuit photovoltage of 762 mV was achieved for the dye JY15 with a 2,2′-bithiophene moiety as the π-bridge using an iodine electrolyte under standard conditions.

Triazatruxene-based organic dyes containing a rhodanine-3-acetic acid acceptor for dye-sensitized solar cells

Co-reporter:Xing Qian, Lin Lu, Yi-Zhou Zhu, Huan-Huan Gao, Jian-Yu Zheng

Dyes and Pigments 2015 Volume 113() pp:737-742

Publication Date(Web):February 2015

DOI:10.1016/j.dyepig.2014.10.007

•Two novel donor-π-acceptor type organic dyes based on triazatruxene were designed and synthesized for DSSCs.•Rhodanine-3-acetic acid was introduced into triazatruxene-based dyes as electron acceptor for the first time.•The dyes exhibited broad IPCE responses up to 800 nm covering almost the whole visible light spectrum.Two novel triazatruxene-based organic dyes with a rhodanine acceptor have been designed, synthesized, and applied as photosensitizers for dye-sensitized solar cells. The photophysical and electrochemical properties of the dyes were investigated using UV–vis absorption spectroscopy, electrochemistry, and density functional theory calculations. Dyes with π-conjugated spacers, thiophene and benzene, both showed broad IPCE responses even up to 800 nm which covers almost the whole visible light spectrum and offers great potential in DSSCs. An overall conversion efficiency of 3.60% under AM 1.5 illumination (100 mW cm−2) was achieved with the benzene spaced dye.

Synthesis of directly fused porphyrin dimers through Fe(OTf)3-mediated oxidative coupling

Co-reporter:Chuan-Mi Feng, Yi-Zhou Zhu, Shao-Chun Zhang, Yun Zang and Jian-Yu Zheng

Organic & Biomolecular Chemistry 2015 vol. 13(Issue 9) pp:2566-2569

Publication Date(Web):12 Jan 2015

DOI:10.1039/C4OB02644F

An efficient and general Fe(OTf)3-mediated oxidative coupling method was developed for the synthesis of doubly or triply linked porphyrin dimers. Besides the central metal and peripheral substituent, regioselectivity of the oxidative coupling was found to be closely relevant to the onset oxidation potential of the porphyrin substrate, and the reactant with higher Eonset(ox) tends to generate meso-β doubly fused porphyrin dimer.

meso-2′-Linked porphyrin–BODIPY hybrids: synthesis and efficient excitation energy transfer

Co-reporter:Qin-Qin Hu, Yi-Zhou Zhu, Shao-Chun Zhang, Yu-Zhang Tong and Jian-Yu Zheng

Dalton Transactions 2015 vol. 44(Issue 35) pp:15523-15530

Publication Date(Web):23 Jul 2015

DOI:10.1039/C5DT01184A

Three meso-2′-linked porphyrin–BODIPY hybrids which contain one, two, and four BODIPY units (BDP–ZnP, 2BDP–ZnP, and 4BDP–ZnP), respectively, were synthesized. Their photophysical properties were investigated by UV-vis and fluorescence spectroscopy, cyclic voltammetry, and femtosecond transient absorption spectroscopy, as well as by theoretical calculations. The electronic properties of the constituent chromophores were found to be largely retained in these hybrids. Meanwhile, efficient and rapid energy transfers from 1BDP* to ZnP were evaluated to be 1.2 × 1011, 1.5 × 1011, and 1.1 × 1011 s−1, respectively.

Biindole-based double D–π–A branched organic dyes for efficient dye-sensitized solar cells

Co-reporter:Xing Qian, Huan-Huan Gao, Yi-Zhou Zhu, Lin Lu and Jian-Yu Zheng

RSC Advances 2015 vol. 5(Issue 6) pp:4368-4375

Publication Date(Web):08 Dec 2014

DOI:10.1039/C4RA12888E

A novel class of double D–π–A branched organic dyes based on 2,2′-disubstituted-1H,1′H-3,3′-biindole moiety have been synthesized, characterized and applied as photosensitizers for dye-sensitized solar cells. Their photophysical, electrochemical and photovoltaic properties are further investigated. These type of organic dyes contain two cyanoacrylic acid moieties as electron acceptors/anchoring groups and different electron-rich conjugated linkers such as furan (JY11), thiophene (JY12) and 2,2′-bithiophene (JY13) as π-bridges. The superiority of the cross X-shaped structure of these double D–π–A branched organic dyes is the suppression of the intermolecular interactions and the guarantee of fast electron injection into the TiO2 semiconductor in the dye-sensitized solar cells. A highest power conversion efficiency of 6.54% was achieved for JY13-based cell with an iodine electrolyte under simulated AM 1.5 G solar irradiation (100 mW cm−2).

Tri(N-carbazolyl)triphenylamine-based starburst organic dyes: effects of different acceptors on the optical, electrochemical and photovoltaic properties

Co-reporter:Xing Qian, Wen-Ying Chang, Yi-Zhou Zhu, Shan-Shan Wang, Bin Pan, Lin Lu and Jian-Yu Zheng

RSC Advances 2015 vol. 5(Issue 59) pp:47422-47428

Publication Date(Web):21 May 2015

DOI:10.1039/C5RA04283F

Two novel tri(N-carbazolyl)triphenylamine-based organic dyes were designed, synthesized and applied as photosensitizers for dye-sensitized solar cells. The superiority of the starburst structure of these dyes is suppressing the intermolecular interactions and guaranteeing a fast electron injection into the TiO2 semiconductor. Cyanoacrylic acid and rhodanine-3-acetic acid were separately used as electron acceptors/anchoring groups to compose the photosensitizers. Different acceptors led to striking changes in the photophysical, electrochemical and photovoltaic properties. An overall power conversion efficiency of 6.53% with a short-circuit photocurrent density of 13.4 mA cm−2, an open-circuit photovoltage of 735 mV and a fill factor of 0.66 was achieved by the dye with tri(N-carbazolyl)triphenylamine as the donor and cyanoacrylic acid as the acceptor under AM 1.5 illumination (100 mW cm−2).

Simple and Catalyst-Free Synthesis of meso-O-, -S-, and -C-Substituted Porphyrins

Co-reporter:Qiang Chen, Yi-Zhou Zhu, Qiao-Jun Fan, Shao-Chun Zhang, and Jian-Yu Zheng

Organic Letters 2014 Volume 16(Issue 6) pp:1590-1593

Publication Date(Web):March 5, 2014

DOI:10.1021/ol500191j

A simple and efficient method for the meso-functionalization of porphyrin has been developed. Kinetic studies of meso-fluoro-, -chloro-, -bromo-, -iodo-, and -nitro-substituted porphyrins (Ni) with phenol reveal that the reaction undergoes a typical aromatic nucleophilic substitution (SNAr) process. This catalyst-free method can be performed with meso-brominated porphyrins and oxygen-, sulfur-, and carbon-based nucleophiles to achieve a wide variety of meso-substituted porphyrins.

Switchable regioselectivity in the PIFA–BF3·Et2O mediated oxidative coupling of meso-brominated Ni(II) porphyrin

Co-reporter:Chuan-Mi Feng, Yi-Zhou Zhu, Yun Zang, Yu-Zhang Tong and Jian-Yu Zheng

Organic & Biomolecular Chemistry 2014 vol. 12(Issue 36) pp:6990-6993

Publication Date(Web):29 Jul 2014

DOI:10.1039/C4OB01517G

A simple and efficient method has been developed for the switchable synthesis of directly linked meso-brominated Ni(II) porphyrin dimers through PIFA–BF3·Et2O mediated oxidative coupling. The respective syntheses of meso–meso or meso–β singly, doubly, and triply linked porphyrin dimers can be easily realized with the same reagent system.

Clawlike Tripodal Porphyrin Trimer: Ion-Controlled On–Off Fullerene Binding

Co-reporter:Xiang Fang, Yi-Zhou Zhu, and Jian-Yu Zheng

The Journal of Organic Chemistry 2014 Volume 79(Issue 3) pp:1184-1191

Publication Date(Web):January 15, 2014

DOI:10.1021/jo4026176

A practical method for the preparation of novel tripodal tris(porphyrinato-urea) TP3 1 was readily achieved. Because of its appreciable preorganized triangular cone-shaped cavity resulting from the intramolecular hydrogen bonds of the tripodal tris-urea backbone, this porphyrin trimer host was found to have a high affinity toward fullerenes to form stable inclusion complexes in solution. A 120-fold binding selectivity toward C70 (Kassoc = 1.81 × 107 M–1) over C60 (Kassoc = 1.51 × 105 M–1) was further achieved in toluene. Moreover, the dissociation of such inclusion complexes can be easily realized by introducing H2PO4–, and recapturing of the fullerene can be achieved after withdrawing H2PO4– by Ca2+. A recyclable process for the inclusion and release of fullerene was therefore built by alternately feeding H2PO4– and Ca2+. Benefiting from this approach, TP3 1 was sequentially applied to isolate C70 from the C60-enriched fullerene mixture successfully.

Metal-Free Iodine(III)-Promoted Synthesis of Isoquinolones

Co-reporter:Zhi-Wei Chen, Yi-Zhou Zhu, Jin-Wang Ou, Ya-Ping Wang, and Jian-Yu Zheng

The Journal of Organic Chemistry 2014 Volume 79(Issue 22) pp:10988-10998

Publication Date(Web):October 24, 2014

DOI:10.1021/jo5020307

A metal-free oxidative cycloaddition reaction of substituted benzamides and alkynes has been developed for the synthesis of isoquinolones by using bis(trifluoracetoxy)iodobenzene (PIFA) and trifluoroacetic acid (TFA). Under mild conditions, a wide variety of isoquinolones were conveniently prepared via oxidative annulation of simple N-methoxybenzamide and diarylacetylene or aryl/alkyl acetylene derivatives in yields up to 87%.

Photophysical properties and potential application in photocurrent generation of porphyrin-[60]fullerene polymer linked by metal axial coordination

Co-reporter:Haiying Zhao, Yizhou Zhu, Chen Chen, Jianyu Zheng

Polymer 2014 Volume 55(Issue 8) pp:1913-1916

Publication Date(Web):10 April 2014

DOI:10.1016/j.polymer.2014.02.058

Porphyrin-[60]fullerene polymers linked by metal axial coordination of fullerenoacetic diacids e-isomer with dihydroxo Sn(IV) porphyrin have been prepared and characterized. The polymers display the regular one-dimensional linear arrays with lengths exceeded 200 nm and show good thermal stability. The efficient photoinduced electron transfer from singlet excited porphyrin to fullerene in the polymer has been achieved resulting in the formation of charge separation state with a lifetime as long as 140 μs in benzonitrile. The long-lived charge separated state is very useful for photoelectric conversion system. The photocurrent generation in organic photovoltaic device was described further, and a steady and rapid cathodic photocurrent response was produced at the irradiation of λex = 429 nm light. The polymers are expected to provide novel photonic or electronic functions in organic solar cell.

New Donor-π-Acceptor Type Triazatruxene Derivatives for Highly Efficient Dye-Sensitized Solar Cells

Co-reporter:Xing Qian, Yi-Zhou Zhu, Jian Song, Xue-Ping Gao, and Jian-Yu Zheng

Organic Letters 2013 Volume 15(Issue 23) pp:6034-6037

Publication Date(Web):November 13, 2013

DOI:10.1021/ol402931u

A new class of organic dyes based on triazatruxene have been designed and synthesized for dye-sensitized solar cells. The photoelectronic properties of these donor-π-acceptor dyes can be tuned by changing π-conjugated linkers. The best performance was found for triazatruxene dye TD1, wherein, with thiophene as the conjugated linker and cyanoacrylic acid as the acceptor, a power conversion efficiency up to 6.10% was achieved.

Syntheses of N-bridged ferrocene/porphyrin-fullerene dyads and influence of iminofullerene isomers on the attached chromophores

Co-reporter:Chen Chen, Yi-Zhou Zhu, Hai-Ying Zhao, Jian-Yu Zheng

Tetrahedron Letters 2013 Volume 54(Issue 12) pp:1607-1611

Publication Date(Web):20 March 2013

DOI:10.1016/j.tetlet.2013.01.061

N-Ferrocene (Fc)/porphyrin (Por) [5,6]-open azafulleroids and [6,6]-closed aziridinofullerenes have been synthesized for the first time. Electrochemical measurements revealed that chromophores attached to [5,6]-open azafulleroids are more easily oxidizable than those attached to [6,6]-closed aziridinofullerenes. This was attributed to the delocalization degree of the nitrogen lone-electron pair involved in aziridinofullerene that is larger than that in azafulleroid.

Syntheses of corrole derivatives and their supramolecular interactions with fullerenes in solution and the solid state

Co-reporter:Chen Chen, Yi-Zhou Zhu, Qiao-Jun Fan, Hai-Bin Song, Jian-Yu Zheng

Tetrahedron Letters 2013 Volume 54(Issue 32) pp:4143-4147

Publication Date(Web):7 August 2013

DOI:10.1016/j.tetlet.2013.05.083

Supramolecular interactions of cobalt corrole and fullerene were investigated both in solution and the solid state. Results reveal that cobalt corrole has the attractive ability to be used as host for fullerene. The cocrystals of cobalt corrole and C60/C70 suitable for X-ray crystallographic analysis were obtained and structure details are discussed.

An Efficient PIFA-Mediated Synthesis of a Directly Linked Zinc Chlorin Dimer via Regioselective Oxidative Coupling

Co-reporter:Qin Ouyang, Kai-Qi Yan, Yi-Zhou Zhu, Cai-Hui Zhang, Jin-Zhong Liu, Chen Chen, and Jian-Yu Zheng

Organic Letters 2012 Volume 14(Issue 11) pp:2746-2749

Publication Date(Web):May 14, 2012

DOI:10.1021/ol300969g

The synthesis of a directly linked zinc chlorin dimer was first achieved by a facile and efficient oxidative coupling of zinc chlorin monomers with phenyliodine bis(trifluoroacetate) (PIFA). The reaction shows high regioselectivity at the 20-position near the hydrogenated pyrrole ring producing selective dichlorin in 74% yield.

Synthesis, characterization, and photophysical properties of covalent-linked ferrocene–porphyrin–single-walled carbon nanotube triad hybrid

Co-reporter:Haiying Zhao, Yizhou Zhu, Chen Chen, Lin He, Jianyu Zheng

Carbon 2012 Volume 50(Issue 13) pp:4894-4902

Publication Date(Web):November 2012

DOI:10.1016/j.carbon.2012.06.018

The ferrocene–porphyrin–single-walled carbon nanotube (Fc–H2P–SWCNT) triad hybrid was prepared by amidation reaction between carboxylated SWCNT and aminoporphyrin bearing an appended ferrocenyl substituent. The hybrid described here was fully characterized by a combination of analytical techniques such as Fourier transform infrared spectroscopy, Raman, absorption and emission spectroscopy, atomic force and scanning electron microscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy. The steady emission characteristics revealed the existence of the effective photoinduced electron transfer among ferrocene, excited porphyrin moiety and SWCNT, which was further confirmed by the results of time-resolved transient absorption spectra. The final lifetime of charge-separation state was observed to be 62.9 μs in N,N-dimethylformamide, which was significant increased compared to the reference nanohybrid porphyrin–SWCNT and the reported ferrocene–porphyrin–fullerene triad. Therefore, Fc–H2P–SWCNT triad hybrid constructed by amidation is rationally expected to be an improved photon-to-electron conversion system.

One-pot synthesis of meso–meso directly linked diheteroporphyrin dimers

Co-reporter:Yi-Zhou Zhu, Yan Zhu, Shao-Chun Zhang, Hai-Bin Song, Jian-Yu Zheng

Tetrahedron Letters 2012 Volume 53(Issue 47) pp:6376-6379

Publication Date(Web):21 November 2012

DOI:10.1016/j.tetlet.2012.09.048

A one-pot synthesis strategy to synthesize the novel meso–meso directly linked dithiaporphyrin dimer (DDSP) was achieved for the first time. And the described methodology also can work smoothly to prepare the oxathiaporphyrin dimers DOSP and DSOP. This work offers a facile and convenient way to get the meso–meso directly linked diheteroporphyrin dimer from simple non-porphyrin precursors.A one-pot synthesis strategy to synthesize the novel meso–meso directly linked dithiaporphyrin dimer (DDSP) was achieved for the first time. And the described methodology also can work smoothly to prepare the oxathiaporphyrin dimers DOSP and DSOP. This work offers a facile and convenient way to get the meso–meso directly linked diheteroporphyrin dimer from simple non-porphyrin precursors.

Synthesis, Photophysical and Electrochemical Properties of Amide-Linked Phthalocyanine-Fullerene Dyad

Co-reporter:Haiying Zhao;Zhibo Liu;Xiaoliang Zhang;Jianguo Tian;Chen Chen;Yizhou Zhu;Jianyu Zheng

Chinese Journal of Chemistry 2012 Volume 30( Issue 8) pp:1766-1770

Publication Date(Web):

DOI:10.1002/cjoc.201200218

Abstract

A new amide-linked phthalocyanine-fullerene dyad ZnPc-C₆₀ was synthesized and characterized. The photophysical and electrochemical properties of the ZnPc-C₆₀ dyad were investigated. The fluorescence spectrum and quantum yield in different solvents showed the occurrence of photoinduced electron transfer (PET) from the singlet excited ZnPc to C₆₀, which was further confirmed by nanosecond transient absorption spectra and cyclic voltammetry data. The free energy change for charge separation (ΔG_CS) was estimated to be exothermic with −0.51 eV, which favored the formation of charge-separation state. The PET from ZnPc to C₆₀ in ZnPc-C₆₀ made the dyad exhibit stronger reverse saturable absorption performance compared with C₆₀ and the control sample in the Z-scan experiments, which indicated the synergistic effect of two active moieties in the dyad.

Synthesis and photophysical properties of polyamides containing in-chain porphyrin and [60]fullerene

Co-reporter:Haiying Zhao;Chen Chen;Yizhou Zhu;Mingzhu Shi

Journal of Nanoparticle Research 2012 Volume 14( Issue 3) pp:

Publication Date(Web):2012 March

DOI:10.1007/s11051-012-0765-0

Conjugated polyamides containing porphyrin and [60]fullerene (C60) in the main chain were prepared by a direct polycondensation of the 3′H,3″H-dicyclopropa[1, 9:16, 17] [5, 6]fullerene-C60-Ih-3′,3″-dicarboxylic acid and 5,15-bis(4-aminophenyl)-10,20-bis(3,5-dialkoxyphenyl)porphyrin in the presence of triphenyl phosphite and pyridine. Gel permeation chromatography (GPC) analysis of the polyamides showed the weight-average molecular weight was about 23,626–23,736, and the temperature at 5% weight loss determined by thermogravimetric analysis (TGA) was above 216 °C. The transmission electron microscopy (TEM) images displayed the regular one-dimensional linear arrays of the polyamides with lengths exceeded 200 nm. The photoinduced electron transfer from porphyrin to C60 in the polyamides was observed in nanosecond laser-flash photolysis experiments at ambient temperature, which produced a charge-separated state (porphyrin radical cation–C60 radical anion pair) with a lifetime as long as 40 μs. The calculated ratio of kCS/kCR was found to be 2.1 × 104. They could have potential applications for photoelectronic devices, organic solar cells and so on.

Meso-meso linked diporphyrin functionalized single-walled carbon nanotubes

Co-reporter:Lin He, Yi-Zhou Zhu, Jian-Yu Zheng, Yan-Feng Ma, Yong-Sheng Chen

Journal of Photochemistry and Photobiology A: Chemistry 2010 Volume 216(Issue 1) pp:15-23

Publication Date(Web):15 November 2010

DOI:10.1016/j.jphotochem.2010.09.001

Meso-meso linked diporphyrins ([H2Por]2) covalently functionalized soluble single-walled carbon nanotubes ([H2Por]2-SWNTs) have been successfully prepared. As a light-harvesting chromophore, meso-meso linked diporphyrins have been incorporated into a photosynthetic electron-transfer model with SWNTs as an electron-acceptor. The steady emission characteristics revealed the existence of the effective energy and electron transfer between the excited porphyrin moiety and SWNTs, and the electron transfer process was confirmed by electrochemical study. The charge separation quenching process was supported by the results of time-resolved transient absorption spectra, and the lifetime of charge-separation state was observed to be 145 ns, which was 2.5 times of that of monoporphyrin modified SWNTs (TPP-SWNTs).

An Efficient PIFA-Mediated Synthesis of Fused Diporphyrin and Triply−Singly Interlacedly Linked Porphyrin Array

Co-reporter:Qin Ouyang, Yi-Zhou Zhu, Cai-Hui Zhang, Kai-Qi Yan, Yun-Chao Li and Jian-Yu Zheng

Organic Letters 2009 Volume 11(Issue 22) pp:5266-5269

Publication Date(Web):October 16, 2009

DOI:10.1021/ol902198w

An efficient and metal-free oxidative method was reported for synthesis of triply linked diporphyrins with 2.5 equiv of phenyliodine bis(trifluoroacetate) (PIFA). This reaction showed high selectivity for Zn(II) porphyrins and had been successfully applied in the synthesis of a novel triply−singly interlacedly linked porphyrin array with lower energy gap.

The cage effect on assembly of cyclic-bis-(zinc porphyrin) with 5,15-dipyridylporphyrin

Co-reporter:ZaiChun Zhou;YiZhou Zhu;JianYu Zheng

Science China Chemistry 2009 Volume 52( Issue 9) pp:1353-1361

Publication Date(Web):2009 September

DOI:10.1007/s11426-009-0207-8

An inclusion complex of cyclic bis(zinc porphyrin) 1 with 5,15-dipyridylporphyrin derivative 3 has been designed and constructed. The complex formation is induced by Zn-N coordination, and is robust (Kassoc ∼ 106 L/mol) due to the presence of the cage effect of cyclic bis(zinc porphyrin). The cage-like complex as an entity is stable enough, and also convenient to achieve relative movement between the bis(zinc porphyrin) host and the dipyridylporphyrin guest connected by Zn-N coordination. The characteristics of these assemblies have been demonstrated by 1 H NMR, UV-vis, and fluorescence spectra. The results show its potential applications as a molecular gyroscope in molecular machines.

Diastereoselective Synthesis of Chiral Diporphyrins via Intramolecular meso−meso Oxidative Coupling

Co-reporter:Qin Ouyang, Yi-Zhou Zhu, Yun-Chao Li, Hui-Bo Wei and Jian-Yu Zheng

The Journal of Organic Chemistry 2009 Volume 74(Issue 8) pp:3164-3167

Publication Date(Web):March 18, 2009

DOI:10.1021/jo9001118

Diastereoselective syntheses of meso−meso linked diporphyrins were achieved via intramolecular chiral induction. The structures and conformations were analyzed by CD, UV, NMR, and computational calculations.

Dynamic Assembly Inclusion Complexes of Tweezer-type Bis(zinc porphyrin) with 5,15-Di(4-pyridyl)porphyrin Derivatives

Co-reporter:Zai-Chun ZHOU;Yi YANG;Yi-Zhou ZHU

Chinese Journal of Chemistry 2008 Volume 26( Issue 10) pp:1913-1921

Publication Date(Web):

DOI:10.1002/cjoc.200890344

Abstract

Dynamic assembly inclusion complexes of tweezer-type bis(zinc porphyrin) (1) with di(4-pyridyl)porphyrin derivatives have been designed and constructed. The complexes are induced by Zn-N coordination, and the weak binding allows the large-size di(4-pyridyl)porphyrin guests in random rotation. Dynamic characteristics of these assemblies, such as ligand exchange and dynamic fluorescence quenching, have been investigated by ¹H NMR, UV-Vis and fluorescence spectra. The stability of such assembly has pronounced dependence on the size-matching effect and thermal effect.

Covalently β-cyclodextrin modified single-walled carbon nanotubes: a novel artificial receptor synthesized by ‘click’ chemistry

Co-reporter:Zhen Guo;Li Liang;Jia-Jie Liang;Yan-Feng Ma

Journal of Nanoparticle Research 2008 Volume 10( Issue 6) pp:1077-1083

Publication Date(Web):2008 August

DOI:10.1007/s11051-007-9338-z

Novel β-cyclodextrin covalently modified single-walled carbon nanotubes have been synthesized via a ‘click’ coupling reaction. The product was fully characterized with Raman, FTIR, XRD, UV-Vis-NIR spectra as well as TEM and TGA measurements. The effective functionalization via ‘click’ coupling has set up a facile and versatile route for modular preparation of SWNTs based functional materials. The inclusion complexation behavior of this artificial receptor with quinine has been investigated in aqueous solution by fluorescence spectroscopy.

Dynamic Assemblies and Photophysical Changes of Zinc Porphyrin Dimer Regulated by N-Containing Ligands

Co-reporter:Zai-Chun ZHOU;Lin HE;Yi-Zhou ZHU

Chinese Journal of Chemistry 2007 Volume 25(Issue 11) pp:1632-1640

Publication Date(Web):13 NOV 2007

DOI:10.1002/cjoc.200790302

Zinc porphyrin dimer (1) has been designed and synthesized as a novel host of N-containing ligands. The assembly behavior and photophysical changes of its host-guest complexes were evaluated by ¹H NMR, fluorescence, and UV-visible titrations, and the processes reveal that the host-guest assembly first creates a stable sandwich complex, then an axial coordination equilibrium appears between the sandwich complex and free ligand. The changes of absorption spectra of the assembly processes rely on the stabilities of the complexes, and fluorescence quenching depends on the axial coordination equilibrium, which indicates that the axial ligation/de-ligation dynamics is indeed a pathway from the excited state to the ground state for metalloporphyrin complexes.

Covalently porphyrin-functionalized single-walled carbon nanotubes: a novel photoactive and optical limiting donor–acceptor nanohybrid

Co-reporter:Zhen Guo, Feng Du, Dongmei Ren, Yongsheng Chen, Jianyu Zheng, Zhibo Liu and Jianguo Tian

Journal of Materials Chemistry A 2006 vol. 16(Issue 29) pp:3021-3030

Publication Date(Web):13 Jun 2006

DOI:10.1039/B602349E

Novel covalently porphyrin-functionalized single-walled carbon nanotubes (SWNTs) have been synthesized by the reaction of SWNTs with in situ generated porphyrin diazonium compounds. The resulting nanohybrid was characterized by spectroscopic (UV-Vis-NIR, FTIR and Raman) and microscopic (TEM and AFM) methods. The Raman and absorption spectroscopy data showed that the electronic properties of the modified tubes were mostly retained, without damaging their one-dimensional electronic properties. The fluorescence from the porphyrin moiety was almost completely quenched by SWNTs, indicating that the unique direct linkage mode facilitated the effective energy and electron transfer between the excited porphyrin moiety and the extended π-system of SWNTs. This novel nanohybrid material also exhibited excellent optical limiting properties.

Fluorescence Quenching Study of Zinc Bisporphyrins by Fulleropyrrolidines and Their N-Oxides

Co-reporter:Hua Xu;Yi Yang;Yi-Zhou Zhu

Chinese Journal of Chemistry 2006 Volume 24(Issue 11) pp:

Publication Date(Web):3 NOV 2006

DOI:10.1002/cjoc.200690297

Novel phenylene-bridged zinc bisporphyrins (1–4), fulleropyrrolidines (C₆₀-m, C₆₀-h) and their N-oxides (C₆₀-mo, C₆₀-ho) were synthesized. The fluorescence quenching processes of bisporphyrins in toluene solution by fulleropyrrolidines and their N-oxides were investigated by steady-state fluorescence spectra. The fluorescence quenching constants proved that the fluorescence quenching ability was decreased as reduction of the pyrrolidine functional groups of fullerene surface: C₆₀-h>C₆₀-m>C₆₀, and the fluorescence quenching ability was increased about 1.3–7.4 times by utilizing fulleropyrrolidine N-oxides (C₆₀-mo, C₆₀-ho) compared to fulleropyrrolidine compounds (C₆₀-m, C₆₀-h). The results revealed photoinduced electron transfer (PET) efficiency between bisporphyrin and fullerene derivatives could be tunable by change of functional groups on fullerene surface.