A Novel Porphyrin-Based Ligand Containing Four 4,4′-Dipyridylamine Moieties: Syntheses, Structures, and Luminescent Properties of Mn(II), Cu(II), Zn(II), and Cd(II) Coordination Polymers

The design and syntheses of porphyrin-based ligands are attractive for creating coordination assemblies with novel structures and intriguing properties. In this work, we designed and synthesized a novel porphyrin-based ligand 5,10,15,20-tetrakis­(4,4′-dipyridylaminophenylene)­porphyrin (TDPAP, H₂L) by the introduction of four peripheral 4,4′-dipyridylamine moieties to a porphyrin platform. Starting from this novel ligand, the protonated form of the ligand H₄LCl₂·2CH₃OH­·2H₂O (<b>1</b>) and four coordination polymers [Mn­(III)­Mn­(II)­LCl₃­(DMF)]_<i>n</i> (<b>2</b>), [Cu₄L­(CH₃COO)₅­(HCOO)­(CH₃COOH)­(H₂O)₃]_<i>n</i>­·<i>n</i>CH₃COOH­·<i>n</i>H₂O (<b>3</b>), [Zn₃L­(CH₃COO)₄]_<i>n</i> (<b>4</b>), and [Cd₂H₂L­(CH₃COO)₄]_<i>n</i>­·<i>n</i>DMF­·<i>n</i>CH₃COOH­·2<i>n</i>H₂O (<b>5</b>) were synthesized. Single crystal X-ray diffraction analyses revealed that a rich structural diversity was observed for these compounds due to the coordination of the multiple peripheral pyridines as well as the porphyrin core. <b>1</b> displays a hydrogen bonded one-dimensional (1D) structure composed of [(H₂O)₂Cl₂]^2– moieties. Complex <b>2</b> shows interpenetrated two-dimensional (2D) coordination networks, which are further linked by π···π stacking interactions to afford a three-dimensional (3D) structure. <b>3</b> shows a 2D sheet composed of 50- and 70-membered metallomacrocycles. In complex <b>4</b>, 1D zigzag coordination chains were generated and further linked to form a 2D structure. Complex <b>5</b> has a stairlike 2D structure formed by the linkage of 1D coordination chains through the bridging of binuclear [Cd₂(CO₂)₄] subunits. In these compounds, TDPAP shows a unique coordination behavior. It may bind 4–7 metal centers, and it demonstrates conformational flexibility and the ability to form intermolecular hydrogen bonds and π···π interactions, which contribute to the formation of novel supramolecular structures. On the basis of the novel structures, the solid state emissions of the compounds were also investigated

A Novel Porphyrin-Based Ligand Containing Four 4,4′-Dipyridylamine Moieties: Syntheses, Structures, and Luminescent Properties of Mn(II), Cu(II), Zn(II), and Cd(II) Coordination Polymers

The design and syntheses of porphyrin-based ligands are attractive for creating coordination assemblies with novel structures and intriguing properties. In this work, we designed and synthesized a novel porphyrin-based ligand 5,10,15,20-tetrakis­(4,4′-dipyridylaminophenylene)­porphyrin (TDPAP, H₂L) by the introduction of four peripheral 4,4′-dipyridylamine moieties to a porphyrin platform. Starting from this novel ligand, the protonated form of the ligand H₄LCl₂·2CH₃OH­·2H₂O (<b>1</b>) and four coordination polymers [Mn­(III)­Mn­(II)­LCl₃­(DMF)]_<i>n</i> (<b>2</b>), [Cu₄L­(CH₃COO)₅­(HCOO)­(CH₃COOH)­(H₂O)₃]_<i>n</i>­·<i>n</i>CH₃COOH­·<i>n</i>H₂O (<b>3</b>), [Zn₃L­(CH₃COO)₄]_<i>n</i> (<b>4</b>), and [Cd₂H₂L­(CH₃COO)₄]_<i>n</i>­·<i>n</i>DMF­·<i>n</i>CH₃COOH­·2<i>n</i>H₂O (<b>5</b>) were synthesized. Single crystal X-ray diffraction analyses revealed that a rich structural diversity was observed for these compounds due to the coordination of the multiple peripheral pyridines as well as the porphyrin core. <b>1</b> displays a hydrogen bonded one-dimensional (1D) structure composed of [(H₂O)₂Cl₂]^2– moieties. Complex <b>2</b> shows interpenetrated two-dimensional (2D) coordination networks, which are further linked by π···π stacking interactions to afford a three-dimensional (3D) structure. <b>3</b> shows a 2D sheet composed of 50- and 70-membered metallomacrocycles. In complex <b>4</b>, 1D zigzag coordination chains were generated and further linked to form a 2D structure. Complex <b>5</b> has a stairlike 2D structure formed by the linkage of 1D coordination chains through the bridging of binuclear [Cd₂(CO₂)₄] subunits. In these compounds, TDPAP shows a unique coordination behavior. It may bind 4–7 metal centers, and it demonstrates conformational flexibility and the ability to form intermolecular hydrogen bonds and π···π interactions, which contribute to the formation of novel supramolecular structures. On the basis of the novel structures, the solid state emissions of the compounds were also investigated

A Novel Porphyrin-Based Ligand Containing Four 4,4′-Dipyridylamine Moieties: Syntheses, Structures, and Luminescent Properties of Mn(II), Cu(II), Zn(II), and Cd(II) Coordination Polymers

The design and syntheses of porphyrin-based ligands are attractive for creating coordination assemblies with novel structures and intriguing properties. In this work, we designed and synthesized a novel porphyrin-based ligand 5,10,15,20-tetrakis­(4,4′-dipyridylaminophenylene)­porphyrin (TDPAP, H₂L) by the introduction of four peripheral 4,4′-dipyridylamine moieties to a porphyrin platform. Starting from this novel ligand, the protonated form of the ligand H₄LCl₂·2CH₃OH­·2H₂O (<b>1</b>) and four coordination polymers [Mn­(III)­Mn­(II)­LCl₃­(DMF)]_<i>n</i> (<b>2</b>), [Cu₄L­(CH₃COO)₅­(HCOO)­(CH₃COOH)­(H₂O)₃]_<i>n</i>­·<i>n</i>CH₃COOH­·<i>n</i>H₂O (<b>3</b>), [Zn₃L­(CH₃COO)₄]_<i>n</i> (<b>4</b>), and [Cd₂H₂L­(CH₃COO)₄]_<i>n</i>­·<i>n</i>DMF­·<i>n</i>CH₃COOH­·2<i>n</i>H₂O (<b>5</b>) were synthesized. Single crystal X-ray diffraction analyses revealed that a rich structural diversity was observed for these compounds due to the coordination of the multiple peripheral pyridines as well as the porphyrin core. <b>1</b> displays a hydrogen bonded one-dimensional (1D) structure composed of [(H₂O)₂Cl₂]^2– moieties. Complex <b>2</b> shows interpenetrated two-dimensional (2D) coordination networks, which are further linked by π···π stacking interactions to afford a three-dimensional (3D) structure. <b>3</b> shows a 2D sheet composed of 50- and 70-membered metallomacrocycles. In complex <b>4</b>, 1D zigzag coordination chains were generated and further linked to form a 2D structure. Complex <b>5</b> has a stairlike 2D structure formed by the linkage of 1D coordination chains through the bridging of binuclear [Cd₂(CO₂)₄] subunits. In these compounds, TDPAP shows a unique coordination behavior. It may bind 4–7 metal centers, and it demonstrates conformational flexibility and the ability to form intermolecular hydrogen bonds and π···π interactions, which contribute to the formation of novel supramolecular structures. On the basis of the novel structures, the solid state emissions of the compounds were also investigated

A Novel Porphyrin-Based Ligand Containing Four 4,4′-Dipyridylamine Moieties: Syntheses, Structures, and Luminescent Properties of Mn(II), Cu(II), Zn(II), and Cd(II) Coordination Polymers

The design and syntheses of porphyrin-based ligands are attractive for creating coordination assemblies with novel structures and intriguing properties. In this work, we designed and synthesized a novel porphyrin-based ligand 5,10,15,20-tetrakis­(4,4′-dipyridylaminophenylene)­porphyrin (TDPAP, H₂L) by the introduction of four peripheral 4,4′-dipyridylamine moieties to a porphyrin platform. Starting from this novel ligand, the protonated form of the ligand H₄LCl₂·2CH₃OH­·2H₂O (<b>1</b>) and four coordination polymers [Mn­(III)­Mn­(II)­LCl₃­(DMF)]_<i>n</i> (<b>2</b>), [Cu₄L­(CH₃COO)₅­(HCOO)­(CH₃COOH)­(H₂O)₃]_<i>n</i>­·<i>n</i>CH₃COOH­·<i>n</i>H₂O (<b>3</b>), [Zn₃L­(CH₃COO)₄]_<i>n</i> (<b>4</b>), and [Cd₂H₂L­(CH₃COO)₄]_<i>n</i>­·<i>n</i>DMF­·<i>n</i>CH₃COOH­·2<i>n</i>H₂O (<b>5</b>) were synthesized. Single crystal X-ray diffraction analyses revealed that a rich structural diversity was observed for these compounds due to the coordination of the multiple peripheral pyridines as well as the porphyrin core. <b>1</b> displays a hydrogen bonded one-dimensional (1D) structure composed of [(H₂O)₂Cl₂]^2– moieties. Complex <b>2</b> shows interpenetrated two-dimensional (2D) coordination networks, which are further linked by π···π stacking interactions to afford a three-dimensional (3D) structure. <b>3</b> shows a 2D sheet composed of 50- and 70-membered metallomacrocycles. In complex <b>4</b>, 1D zigzag coordination chains were generated and further linked to form a 2D structure. Complex <b>5</b> has a stairlike 2D structure formed by the linkage of 1D coordination chains through the bridging of binuclear [Cd₂(CO₂)₄] subunits. In these compounds, TDPAP shows a unique coordination behavior. It may bind 4–7 metal centers, and it demonstrates conformational flexibility and the ability to form intermolecular hydrogen bonds and π···π interactions, which contribute to the formation of novel supramolecular structures. On the basis of the novel structures, the solid state emissions of the compounds were also investigated

A Novel Porphyrin-Based Ligand Containing Four 4,4′-Dipyridylamine Moieties: Syntheses, Structures, and Luminescent Properties of Mn(II), Cu(II), Zn(II), and Cd(II) Coordination Polymers

The design and syntheses of porphyrin-based ligands are attractive for creating coordination assemblies with novel structures and intriguing properties. In this work, we designed and synthesized a novel porphyrin-based ligand 5,10,15,20-tetrakis­(4,4′-dipyridylaminophenylene)­porphyrin (TDPAP, H₂L) by the introduction of four peripheral 4,4′-dipyridylamine moieties to a porphyrin platform. Starting from this novel ligand, the protonated form of the ligand H₄LCl₂·2CH₃OH­·2H₂O (<b>1</b>) and four coordination polymers [Mn­(III)­Mn­(II)­LCl₃­(DMF)]_<i>n</i> (<b>2</b>), [Cu₄L­(CH₃COO)₅­(HCOO)­(CH₃COOH)­(H₂O)₃]_<i>n</i>­·<i>n</i>CH₃COOH­·<i>n</i>H₂O (<b>3</b>), [Zn₃L­(CH₃COO)₄]_<i>n</i> (<b>4</b>), and [Cd₂H₂L­(CH₃COO)₄]_<i>n</i>­·<i>n</i>DMF­·<i>n</i>CH₃COOH­·2<i>n</i>H₂O (<b>5</b>) were synthesized. Single crystal X-ray diffraction analyses revealed that a rich structural diversity was observed for these compounds due to the coordination of the multiple peripheral pyridines as well as the porphyrin core. <b>1</b> displays a hydrogen bonded one-dimensional (1D) structure composed of [(H₂O)₂Cl₂]^2– moieties. Complex <b>2</b> shows interpenetrated two-dimensional (2D) coordination networks, which are further linked by π···π stacking interactions to afford a three-dimensional (3D) structure. <b>3</b> shows a 2D sheet composed of 50- and 70-membered metallomacrocycles. In complex <b>4</b>, 1D zigzag coordination chains were generated and further linked to form a 2D structure. Complex <b>5</b> has a stairlike 2D structure formed by the linkage of 1D coordination chains through the bridging of binuclear [Cd₂(CO₂)₄] subunits. In these compounds, TDPAP shows a unique coordination behavior. It may bind 4–7 metal centers, and it demonstrates conformational flexibility and the ability to form intermolecular hydrogen bonds and π···π interactions, which contribute to the formation of novel supramolecular structures. On the basis of the novel structures, the solid state emissions of the compounds were also investigated

Polynuclear Complexes of Ligands Containing in Situ Formed Oxazinane and Oxazolidine Rings with Appended Alkoxyl and Phenol Groups

In situ formation of ligands is an efficient approach to synthesizing novel complexes with unique coordinating moieties. Oxazolidines and oxazinanes are 1,3-N,O-containing five-membered and six-membered heterocycles, respectively. Metal complexes of ligands derived from these two heterocycles are rather rare. In this work, we designed and synthesized a novel multihydoxy ligand, 2-((2,3-dihydroxypropylamino)­methyl)­phenol (H₃L¹). It contains both aminoethanol and aminopropanol units, which may be employed to react with aldehydes to afford oxazolidines and oxazinanes, respectively. Thus, H₃L¹ was reacted with metal salts in the absence or presence of aldehydes to afford complexes [Cu­(HL¹)]₂ (<b>1</b>), [CuL²]₄·4CH₃OH (<b>2</b>) [Zn₅Na₂(L³)₄­(DMSO)_2.65­(DMF)_1.35]­·DMF (<b>3</b>), and [Ni­(HL⁴)]₂ (<b>4</b>). Complex <b>1</b> is a dialkoxo-bridged binuclear Cu­(II) complex. The coordination moieties are linked by intermolecular C–H···O hydrogen bonds to afford a 1D double-chain supramolecular structure. Interestingly, in complexes <b>2</b>–<b>4</b>, H₃L¹ has been reacted with formaldehyde, salicylaldehyde, and 2,6-diformyl-4-cresol to afford novel ligands H₂L², H₃L³, and H₃L⁴, respectively. The combination of in situ formed oxazinane or oxazolidine rings with appended alkoxyl and phenol functionalities in these ligands has been demonstrated to form a rich diversity of coordination structures. Thus, <b>2</b> is a tetranuclear Cu­(II) complex with a face-sharing double defective cubane core structure. In this complex, (L²)^2– ligands coordinate in two different bridging modes with the Harris notations of 3.1₁2₁₂2₁₃1₁ and 3.1₁3₁₂₃1₁1₁, respectively. Complex <b>3</b> has an interesting heptanuclear Zn₅Na₂ core structure. A central Zn­(II) is coordinated with four alkoxo O atoms from four (L³)^3– ligands. Each of the O atom further bridges another Zn­(II) atom, resulting in a Zn₅ moiety, which is then connected to two Na⁺ by phenoxo O bridges, finally affording the Zn₅Na₂ core. The bridging mode of (L³)^3– can be designated as 4.2₁₂2₁₃1₁3₁₂₄1₁. And Complex <b>4</b> is a binuclear Ni­(II) complex containing di-μ₂-phenoxo bridges. The coordination moieties are linked by intermolecular C–H···π, C–H···O, and π···π interactions to afford a two-dimensional supramolecular network. These results indicate that the combination of in situ formed oxazinane and oxazolidine rings with appended phenol and alkoxyl functionalities is an efficient approach to developing novel ligands and complexes with a rich structural diversity. Variable temperature magnetic data measurements revealed that medium antiferromagnetic interaction exists between the Cu­(II) centers in complex <b>1</b> with a −2<i>J</i> value of 278 cm^–1. And in complex <b>4</b>, weak antiferromagnetic coupling occurs between the Ni­(II) centers, with a −2<i>J</i> value of 9.36 cm^–1

Polynuclear Complexes of Ligands Containing in Situ Formed Oxazinane and Oxazolidine Rings with Appended Alkoxyl and Phenol Groups

In situ formation of ligands is an efficient approach to synthesizing novel complexes with unique coordinating moieties. Oxazolidines and oxazinanes are 1,3-N,O-containing five-membered and six-membered heterocycles, respectively. Metal complexes of ligands derived from these two heterocycles are rather rare. In this work, we designed and synthesized a novel multihydoxy ligand, 2-((2,3-dihydroxypropylamino)­methyl)­phenol (H₃L¹). It contains both aminoethanol and aminopropanol units, which may be employed to react with aldehydes to afford oxazolidines and oxazinanes, respectively. Thus, H₃L¹ was reacted with metal salts in the absence or presence of aldehydes to afford complexes [Cu­(HL¹)]₂ (<b>1</b>), [CuL²]₄·4CH₃OH (<b>2</b>) [Zn₅Na₂(L³)₄­(DMSO)_2.65­(DMF)_1.35]­·DMF (<b>3</b>), and [Ni­(HL⁴)]₂ (<b>4</b>). Complex <b>1</b> is a dialkoxo-bridged binuclear Cu­(II) complex. The coordination moieties are linked by intermolecular C–H···O hydrogen bonds to afford a 1D double-chain supramolecular structure. Interestingly, in complexes <b>2</b>–<b>4</b>, H₃L¹ has been reacted with formaldehyde, salicylaldehyde, and 2,6-diformyl-4-cresol to afford novel ligands H₂L², H₃L³, and H₃L⁴, respectively. The combination of in situ formed oxazinane or oxazolidine rings with appended alkoxyl and phenol functionalities in these ligands has been demonstrated to form a rich diversity of coordination structures. Thus, <b>2</b> is a tetranuclear Cu­(II) complex with a face-sharing double defective cubane core structure. In this complex, (L²)^2– ligands coordinate in two different bridging modes with the Harris notations of 3.1₁2₁₂2₁₃1₁ and 3.1₁3₁₂₃1₁1₁, respectively. Complex <b>3</b> has an interesting heptanuclear Zn₅Na₂ core structure. A central Zn­(II) is coordinated with four alkoxo O atoms from four (L³)^3– ligands. Each of the O atom further bridges another Zn­(II) atom, resulting in a Zn₅ moiety, which is then connected to two Na⁺ by phenoxo O bridges, finally affording the Zn₅Na₂ core. The bridging mode of (L³)^3– can be designated as 4.2₁₂2₁₃1₁3₁₂₄1₁. And Complex <b>4</b> is a binuclear Ni­(II) complex containing di-μ₂-phenoxo bridges. The coordination moieties are linked by intermolecular C–H···π, C–H···O, and π···π interactions to afford a two-dimensional supramolecular network. These results indicate that the combination of in situ formed oxazinane and oxazolidine rings with appended phenol and alkoxyl functionalities is an efficient approach to developing novel ligands and complexes with a rich structural diversity. Variable temperature magnetic data measurements revealed that medium antiferromagnetic interaction exists between the Cu­(II) centers in complex <b>1</b> with a −2<i>J</i> value of 278 cm^–1. And in complex <b>4</b>, weak antiferromagnetic coupling occurs between the Ni­(II) centers, with a −2<i>J</i> value of 9.36 cm^–1

α‑Monoacylated and α,α′- and α,β′-Diacylated Dipyrrins as Highly Sensitive Fluorescence “Turn-on” Zn²⁺ Probes

With the purpose of developing readily synthesized CHEF (chelation-enhanced fluorescence) type Zn²⁺ probes with relatively simple molecular structures and excellent sensing behavior, <i>p</i>-anisoyl chloride was used for the acylation of 5-(penta­fluoro­phenyl)­dipyrro­methane. Interestingly, the α,β′-diacylated product <b>PS2</b> with a unique substitution mode was obtained in high yield in addition to the normal α-substituted mono- and diacylated products <b>PS1</b> and <b>PS3</b>. Further oxidation of <b>PS1</b>–<b>PS3</b> afforded dipyrrins <b>S1</b>–<b>S3</b>. Crystal structure and ¹H NMR measurements of <b>S2</b> demonstrate the existence of a pure tautomer, which is consistent with DFT calculations. <b>S1</b>–<b>S3</b> show highly Zn²⁺ selective “turn-on” fluorescence based on a CHEF mechanism by the formation of 2:1 (probe:metal) Zn²⁺ complexes. The emission colors can be easily tuned from green to red by changing the dipyrrin substitution modes. Furthermore, these probes demonstrate fast responses and wide applicable pH ranges. Among them, <b>S2</b> shows the highest Zn²⁺ sensitivity, with a detection limit of 4.4 × 10^–8 M

Efficient Solar Cells Based on Porphyrin Dyes with Flexible Chains Attached to the Auxiliary Benzothiadiazole Acceptor: Suppression of Dye Aggregation and the Effect of Distortion

Donor−π–acceptor-type porphyrin dyes have been widely used for the fabrication of efficient dye-sensitized solar cells (DSSCs) owing to their strong absorption in the visible region and the ease of modifying their chemical structures and photovoltaic behavior. On the basis of our previously reported efficient porphyrin dye <b>XW11</b>, which contains a phenothiazine-based electron donor, a π-extending ethynylene unit, and an auxiliary benzothiadiazole acceptor, we herein report the syntheses of novel porphyrin dyes <b>XW26</b>–<b>XW28</b> by introducing one or two alkyl/alkoxy chains into the auxiliary acceptor. The introduced chains can effectively suppress dye aggregation. As a result, <b>XW26</b>–<b>XW28</b> show excellent photovoltages of 700, 701, and 711 mV, respectively, obviously higher than 645 mV obtained for <b>XW11</b>. Nevertheless, the optimized structures of <b>XW26</b> and <b>XW27</b> exhibit severe distortion, showing large dihedral angles of 57.2° and 44.0°, respectively, between the benzothiadiazole and benzoic acid units, resulting from the steric hindrance between the benzoic acid unit and the neighboring alkyl/alkoxy chain on the benzothiadiazole unit, and thus blue-shifted absorption, decreased photocurrents. and low efficiencies of 5.19% and 6.42% were observed for <b>XW26</b> and <b>XW27</b>, respectively. Interestingly, <b>XW26</b> exhibits a more blue-shifted absorption spectrum relative to <b>XW27</b>, indicating that the steric hindrance of the alkyl/alkoxy chains has a more pronounced effect than the electronic effect. Different from <b>XW26</b> and <b>XW27</b>, <b>XW28</b> contains only one alkyl chain neighboring the ethynylene unit, which does not induce obvious steric hindrance with the benzoic acid unit, and thus distortion of the molecule is not seriously aggravated compared with <b>XW11</b>. Hence, its absorption spectrum and photocurrent are similar to those of <b>XW11</b>. As a result, a higher efficiency of 9.12% was achieved for <b>XW28</b> because of its suppressed dye aggregation and higher photovoltage. It is worth noting that a high efficiency of 10.14% was successfully achieved for <b>XW28</b> upon coadsorption with CDCA, which is also higher than the corresponding efficiency obtained for <b>XW11</b>. These results provide a novel approach for developing efficient porphyrin dyes by introducing chains into the suitable position of the auxiliary benzothiadiazolyl moiety to suppress dye aggregation, without seriously aggravating distortion of the dye molecules

Oxidative Ring Closure and Metal Triggered Ring Opening: Syntheses of Macrocyclic and Linear Hexapyrroles

A C₆F₅-substituted hexapyrrane (<b>1</b>) was synthesized in one step. Oxidative cyclization of <b>1</b> with DDQ afforded a phlorin–dipyrrin conjugate (<b>2</b>), and subsequent FeCl₃-assisted oxidative cleavage of <b>2</b> afforded a terminally di-α-methoxy substituted hexapyrrin (<b>3</b>). On the other hand, oxidation of <b>1</b> with FeCl₃ afforded <b>3</b>, a hexapyrrinone Fe³⁺ complex (<b>4</b>), and a hexaphyrin (1,1,1,1,1,0) (<b>5</b>). These results indicate that the oxidation of hexapyrranes may be developed as an effective approach for the syntheses of novel linear and macrocyclic hexapyrroles