Transformation of a Mother Crystal to a Daughter Crystal through Amorphous Phase: De-assembly of Coordination Helices upon Heating and Re-assembly through Aquation

The nonlinear optical active chiral complex <b>1</b> [{Co­(2,5-pdc)­(H₂O)₂}­H₂O]_<i>n</i> (2,5-pdc = 2,5-pyridine dicarboxylate) has been synthesized via a solvothermal technique using the achiral 2,5-pdc ligand. Complex <b>1</b> (phase <b>1</b>), a two-dimensional coordination polymer, undergoes crystalline to amorphous (phase <b>2</b>) transformation upon deaquation, which under reaquation generates a new microcrystalline phase (phase <b>3</b>). The crystal structure of phase <b>3</b> has been determined by powder X-ray diffraction analysis (PXRD), which reveals that the resultant microcrystalline phase <b>3</b> is an achiral complex consisting of one-dimensional coordination chains. Phase <b>3</b> undergoes reversible structural transformation via amorphous phase (phase <b>2</b>) upon dehydration and subsequent rehydration. This amorphous phase shows selective adsorption of water from a water–DMF mixture and water–CCl₄ mixture. Phase <b>1</b> to phase <b>3</b> structural transformation proceeds through selective bond breaking. The magnetic studies of the two crystalline and the amorphous phase reveal that phase <b>1</b> behaves as a canted antiferromagnet, while both amorphous phase <b>2</b> and phase <b>3</b> show antiferromagnetism

Transformation of a Mother Crystal to a Daughter Crystal through Amorphous Phase: De-assembly of Coordination Helices upon Heating and Re-assembly through Aquation

The nonlinear optical active chiral complex <b>1</b> [{Co­(2,5-pdc)­(H₂O)₂}­H₂O]_<i>n</i> (2,5-pdc = 2,5-pyridine dicarboxylate) has been synthesized via a solvothermal technique using the achiral 2,5-pdc ligand. Complex <b>1</b> (phase <b>1</b>), a two-dimensional coordination polymer, undergoes crystalline to amorphous (phase <b>2</b>) transformation upon deaquation, which under reaquation generates a new microcrystalline phase (phase <b>3</b>). The crystal structure of phase <b>3</b> has been determined by powder X-ray diffraction analysis (PXRD), which reveals that the resultant microcrystalline phase <b>3</b> is an achiral complex consisting of one-dimensional coordination chains. Phase <b>3</b> undergoes reversible structural transformation via amorphous phase (phase <b>2</b>) upon dehydration and subsequent rehydration. This amorphous phase shows selective adsorption of water from a water–DMF mixture and water–CCl₄ mixture. Phase <b>1</b> to phase <b>3</b> structural transformation proceeds through selective bond breaking. The magnetic studies of the two crystalline and the amorphous phase reveal that phase <b>1</b> behaves as a canted antiferromagnet, while both amorphous phase <b>2</b> and phase <b>3</b> show antiferromagnetism

Transformation of a Mother Crystal to a Daughter Crystal through Amorphous Phase: De-assembly of Coordination Helices upon Heating and Re-assembly through Aquation

The nonlinear optical active chiral complex <b>1</b> [{Co­(2,5-pdc)­(H₂O)₂}­H₂O]_<i>n</i> (2,5-pdc = 2,5-pyridine dicarboxylate) has been synthesized via a solvothermal technique using the achiral 2,5-pdc ligand. Complex <b>1</b> (phase <b>1</b>), a two-dimensional coordination polymer, undergoes crystalline to amorphous (phase <b>2</b>) transformation upon deaquation, which under reaquation generates a new microcrystalline phase (phase <b>3</b>). The crystal structure of phase <b>3</b> has been determined by powder X-ray diffraction analysis (PXRD), which reveals that the resultant microcrystalline phase <b>3</b> is an achiral complex consisting of one-dimensional coordination chains. Phase <b>3</b> undergoes reversible structural transformation via amorphous phase (phase <b>2</b>) upon dehydration and subsequent rehydration. This amorphous phase shows selective adsorption of water from a water–DMF mixture and water–CCl₄ mixture. Phase <b>1</b> to phase <b>3</b> structural transformation proceeds through selective bond breaking. The magnetic studies of the two crystalline and the amorphous phase reveal that phase <b>1</b> behaves as a canted antiferromagnet, while both amorphous phase <b>2</b> and phase <b>3</b> show antiferromagnetism

Tetrabromoterepthalic Acid in Designing Co-crystals and Salts: Modification of Optical Properties and Schottky Barrier Effect

Herein, tetrabromoterepthalic acid (TBTA) is used as the potential co-crystal former with various organic base molecules containing free nitrogen atoms. The crystal structure of TBTA (compound <b>1</b>) has been determined from powder X-ray diffraction (PXRD) data. In a systematic way, we have synthesized hydrated-TBTA (compound <b>2</b>), two salts of TBTA [TBTA^2––4,4′-bipy²⁺ (compound <b>3</b>), 4,4′-bipy = 4,4′-bipyridine, and TBTA^2––(3-AP⁺)₂ (compound <b>4</b>), 3-AP = 3-aminopyridine] and two co-crystals of TBTA [TBTA–DPTZ (compound <b>5</b>), DPTZ = 3,6-di­(pyridyl-2-yl)-1,2,4,5-tetrazine, and TBTA–(3-IP)₂ (compound <b>6</b>), 3-IP = 3-iodopyridine]. All of the compounds were characterized by structural, spectral, and thermal studies. Supramolecular structural analysis reveals that <b>1</b> forms a 2D supramolecular sheet structure by means of O–H···Br hydrogen bonding interactions and hydrated-<b>2</b> forms a 3D supramolecular structure through water mediated hydrogen bonding interactions and π··· interactions. The O–H···N/O¯···H–N⁺ hydrogen bonding interactions between acid and base molecules give rise to 1D supramolecular chain structure in <b>3</b> and supramolecular trimers in <b>4</b>, <b>5</b>, and <b>6</b>. Because of presence of charge assisted O^¯···H–N⁺ hydrogen bonds between acid–base molecules, <b>3</b> and <b>4</b> form hydrogen bonds with solvent water molecules, and also both <b>3</b> and <b>4</b> form 3D supramolecular structures using both hydrogen bonding and π··· interactions. In co-crystal <b>5</b>, solvent water molecules participate in crystallization in contrast to <b>6</b>, and it has been observed that <b>5</b> forms 3D supramolecular structure, while <b>6</b> forms 2D supramolecular structure using both hydrogen bonding and π··· interactions. An investigation of intermolecular closed contacts has been carried out by Hirshfeld surface analysis, and associated 2D fingerprint plots reveal the similarities and differences of TBTA molecules in these six crystal structures. Photoluminescence spectra of all the compounds have been studied, and they reveal that with change of polarity around TBTA luminescent intensity of the compounds has been modified. <i>I</i>–<i>V</i> measurement indicates that <b>3</b> shows semiconducting behavior, and the ITO/<b>3</b>/Al sandwich structure acts as a Schottky barrier diode. The device exhibits an excellent rectification ratio (19 at ±1 V) with an ideality factor of 2.96. The semiconducting behavior of <b>3</b> is attributed to the formation charge assisted hydrogen bonding interactions between acid and base molecules

Tetrabromoterepthalic Acid in Designing Co-crystals and Salts: Modification of Optical Properties and Schottky Barrier Effect

Herein, tetrabromoterepthalic acid (TBTA) is used as the potential co-crystal former with various organic base molecules containing free nitrogen atoms. The crystal structure of TBTA (compound <b>1</b>) has been determined from powder X-ray diffraction (PXRD) data. In a systematic way, we have synthesized hydrated-TBTA (compound <b>2</b>), two salts of TBTA [TBTA^2––4,4′-bipy²⁺ (compound <b>3</b>), 4,4′-bipy = 4,4′-bipyridine, and TBTA^2––(3-AP⁺)₂ (compound <b>4</b>), 3-AP = 3-aminopyridine] and two co-crystals of TBTA [TBTA–DPTZ (compound <b>5</b>), DPTZ = 3,6-di­(pyridyl-2-yl)-1,2,4,5-tetrazine, and TBTA–(3-IP)₂ (compound <b>6</b>), 3-IP = 3-iodopyridine]. All of the compounds were characterized by structural, spectral, and thermal studies. Supramolecular structural analysis reveals that <b>1</b> forms a 2D supramolecular sheet structure by means of O–H···Br hydrogen bonding interactions and hydrated-<b>2</b> forms a 3D supramolecular structure through water mediated hydrogen bonding interactions and π··· interactions. The O–H···N/O¯···H–N⁺ hydrogen bonding interactions between acid and base molecules give rise to 1D supramolecular chain structure in <b>3</b> and supramolecular trimers in <b>4</b>, <b>5</b>, and <b>6</b>. Because of presence of charge assisted O^¯···H–N⁺ hydrogen bonds between acid–base molecules, <b>3</b> and <b>4</b> form hydrogen bonds with solvent water molecules, and also both <b>3</b> and <b>4</b> form 3D supramolecular structures using both hydrogen bonding and π··· interactions. In co-crystal <b>5</b>, solvent water molecules participate in crystallization in contrast to <b>6</b>, and it has been observed that <b>5</b> forms 3D supramolecular structure, while <b>6</b> forms 2D supramolecular structure using both hydrogen bonding and π··· interactions. An investigation of intermolecular closed contacts has been carried out by Hirshfeld surface analysis, and associated 2D fingerprint plots reveal the similarities and differences of TBTA molecules in these six crystal structures. Photoluminescence spectra of all the compounds have been studied, and they reveal that with change of polarity around TBTA luminescent intensity of the compounds has been modified. <i>I</i>–<i>V</i> measurement indicates that <b>3</b> shows semiconducting behavior, and the ITO/<b>3</b>/Al sandwich structure acts as a Schottky barrier diode. The device exhibits an excellent rectification ratio (19 at ±1 V) with an ideality factor of 2.96. The semiconducting behavior of <b>3</b> is attributed to the formation charge assisted hydrogen bonding interactions between acid and base molecules

Tetrabromoterepthalic Acid in Designing Co-crystals and Salts: Modification of Optical Properties and Schottky Barrier Effect

Herein, tetrabromoterepthalic acid (TBTA) is used as the potential co-crystal former with various organic base molecules containing free nitrogen atoms. The crystal structure of TBTA (compound <b>1</b>) has been determined from powder X-ray diffraction (PXRD) data. In a systematic way, we have synthesized hydrated-TBTA (compound <b>2</b>), two salts of TBTA [TBTA^2––4,4′-bipy²⁺ (compound <b>3</b>), 4,4′-bipy = 4,4′-bipyridine, and TBTA^2––(3-AP⁺)₂ (compound <b>4</b>), 3-AP = 3-aminopyridine] and two co-crystals of TBTA [TBTA–DPTZ (compound <b>5</b>), DPTZ = 3,6-di­(pyridyl-2-yl)-1,2,4,5-tetrazine, and TBTA–(3-IP)₂ (compound <b>6</b>), 3-IP = 3-iodopyridine]. All of the compounds were characterized by structural, spectral, and thermal studies. Supramolecular structural analysis reveals that <b>1</b> forms a 2D supramolecular sheet structure by means of O–H···Br hydrogen bonding interactions and hydrated-<b>2</b> forms a 3D supramolecular structure through water mediated hydrogen bonding interactions and π··· interactions. The O–H···N/O¯···H–N⁺ hydrogen bonding interactions between acid and base molecules give rise to 1D supramolecular chain structure in <b>3</b> and supramolecular trimers in <b>4</b>, <b>5</b>, and <b>6</b>. Because of presence of charge assisted O^¯···H–N⁺ hydrogen bonds between acid–base molecules, <b>3</b> and <b>4</b> form hydrogen bonds with solvent water molecules, and also both <b>3</b> and <b>4</b> form 3D supramolecular structures using both hydrogen bonding and π··· interactions. In co-crystal <b>5</b>, solvent water molecules participate in crystallization in contrast to <b>6</b>, and it has been observed that <b>5</b> forms 3D supramolecular structure, while <b>6</b> forms 2D supramolecular structure using both hydrogen bonding and π··· interactions. An investigation of intermolecular closed contacts has been carried out by Hirshfeld surface analysis, and associated 2D fingerprint plots reveal the similarities and differences of TBTA molecules in these six crystal structures. Photoluminescence spectra of all the compounds have been studied, and they reveal that with change of polarity around TBTA luminescent intensity of the compounds has been modified. <i>I</i>–<i>V</i> measurement indicates that <b>3</b> shows semiconducting behavior, and the ITO/<b>3</b>/Al sandwich structure acts as a Schottky barrier diode. The device exhibits an excellent rectification ratio (19 at ±1 V) with an ideality factor of 2.96. The semiconducting behavior of <b>3</b> is attributed to the formation charge assisted hydrogen bonding interactions between acid and base molecules

Tetrabromoterepthalic Acid in Designing Co-crystals and Salts: Modification of Optical Properties and Schottky Barrier Effect

Herein, tetrabromoterepthalic acid (TBTA) is used as the potential co-crystal former with various organic base molecules containing free nitrogen atoms. The crystal structure of TBTA (compound <b>1</b>) has been determined from powder X-ray diffraction (PXRD) data. In a systematic way, we have synthesized hydrated-TBTA (compound <b>2</b>), two salts of TBTA [TBTA^2––4,4′-bipy²⁺ (compound <b>3</b>), 4,4′-bipy = 4,4′-bipyridine, and TBTA^2––(3-AP⁺)₂ (compound <b>4</b>), 3-AP = 3-aminopyridine] and two co-crystals of TBTA [TBTA–DPTZ (compound <b>5</b>), DPTZ = 3,6-di­(pyridyl-2-yl)-1,2,4,5-tetrazine, and TBTA–(3-IP)₂ (compound <b>6</b>), 3-IP = 3-iodopyridine]. All of the compounds were characterized by structural, spectral, and thermal studies. Supramolecular structural analysis reveals that <b>1</b> forms a 2D supramolecular sheet structure by means of O–H···Br hydrogen bonding interactions and hydrated-<b>2</b> forms a 3D supramolecular structure through water mediated hydrogen bonding interactions and π··· interactions. The O–H···N/O¯···H–N⁺ hydrogen bonding interactions between acid and base molecules give rise to 1D supramolecular chain structure in <b>3</b> and supramolecular trimers in <b>4</b>, <b>5</b>, and <b>6</b>. Because of presence of charge assisted O^¯···H–N⁺ hydrogen bonds between acid–base molecules, <b>3</b> and <b>4</b> form hydrogen bonds with solvent water molecules, and also both <b>3</b> and <b>4</b> form 3D supramolecular structures using both hydrogen bonding and π··· interactions. In co-crystal <b>5</b>, solvent water molecules participate in crystallization in contrast to <b>6</b>, and it has been observed that <b>5</b> forms 3D supramolecular structure, while <b>6</b> forms 2D supramolecular structure using both hydrogen bonding and π··· interactions. An investigation of intermolecular closed contacts has been carried out by Hirshfeld surface analysis, and associated 2D fingerprint plots reveal the similarities and differences of TBTA molecules in these six crystal structures. Photoluminescence spectra of all the compounds have been studied, and they reveal that with change of polarity around TBTA luminescent intensity of the compounds has been modified. <i>I</i>–<i>V</i> measurement indicates that <b>3</b> shows semiconducting behavior, and the ITO/<b>3</b>/Al sandwich structure acts as a Schottky barrier diode. The device exhibits an excellent rectification ratio (19 at ±1 V) with an ideality factor of 2.96. The semiconducting behavior of <b>3</b> is attributed to the formation charge assisted hydrogen bonding interactions between acid and base molecules

Tetrabromoterepthalic Acid in Designing Co-crystals and Salts: Modification of Optical Properties and Schottky Barrier Effect

Herein, tetrabromoterepthalic acid (TBTA) is used as the potential co-crystal former with various organic base molecules containing free nitrogen atoms. The crystal structure of TBTA (compound <b>1</b>) has been determined from powder X-ray diffraction (PXRD) data. In a systematic way, we have synthesized hydrated-TBTA (compound <b>2</b>), two salts of TBTA [TBTA^2––4,4′-bipy²⁺ (compound <b>3</b>), 4,4′-bipy = 4,4′-bipyridine, and TBTA^2––(3-AP⁺)₂ (compound <b>4</b>), 3-AP = 3-aminopyridine] and two co-crystals of TBTA [TBTA–DPTZ (compound <b>5</b>), DPTZ = 3,6-di­(pyridyl-2-yl)-1,2,4,5-tetrazine, and TBTA–(3-IP)₂ (compound <b>6</b>), 3-IP = 3-iodopyridine]. All of the compounds were characterized by structural, spectral, and thermal studies. Supramolecular structural analysis reveals that <b>1</b> forms a 2D supramolecular sheet structure by means of O–H···Br hydrogen bonding interactions and hydrated-<b>2</b> forms a 3D supramolecular structure through water mediated hydrogen bonding interactions and π··· interactions. The O–H···N/O¯···H–N⁺ hydrogen bonding interactions between acid and base molecules give rise to 1D supramolecular chain structure in <b>3</b> and supramolecular trimers in <b>4</b>, <b>5</b>, and <b>6</b>. Because of presence of charge assisted O^¯···H–N⁺ hydrogen bonds between acid–base molecules, <b>3</b> and <b>4</b> form hydrogen bonds with solvent water molecules, and also both <b>3</b> and <b>4</b> form 3D supramolecular structures using both hydrogen bonding and π··· interactions. In co-crystal <b>5</b>, solvent water molecules participate in crystallization in contrast to <b>6</b>, and it has been observed that <b>5</b> forms 3D supramolecular structure, while <b>6</b> forms 2D supramolecular structure using both hydrogen bonding and π··· interactions. An investigation of intermolecular closed contacts has been carried out by Hirshfeld surface analysis, and associated 2D fingerprint plots reveal the similarities and differences of TBTA molecules in these six crystal structures. Photoluminescence spectra of all the compounds have been studied, and they reveal that with change of polarity around TBTA luminescent intensity of the compounds has been modified. <i>I</i>–<i>V</i> measurement indicates that <b>3</b> shows semiconducting behavior, and the ITO/<b>3</b>/Al sandwich structure acts as a Schottky barrier diode. The device exhibits an excellent rectification ratio (19 at ±1 V) with an ideality factor of 2.96. The semiconducting behavior of <b>3</b> is attributed to the formation charge assisted hydrogen bonding interactions between acid and base molecules

Tetrabromoterepthalic Acid in Designing Co-crystals and Salts: Modification of Optical Properties and Schottky Barrier Effect

Herein, tetrabromoterepthalic acid (TBTA) is used as the potential co-crystal former with various organic base molecules containing free nitrogen atoms. The crystal structure of TBTA (compound <b>1</b>) has been determined from powder X-ray diffraction (PXRD) data. In a systematic way, we have synthesized hydrated-TBTA (compound <b>2</b>), two salts of TBTA [TBTA^2––4,4′-bipy²⁺ (compound <b>3</b>), 4,4′-bipy = 4,4′-bipyridine, and TBTA^2––(3-AP⁺)₂ (compound <b>4</b>), 3-AP = 3-aminopyridine] and two co-crystals of TBTA [TBTA–DPTZ (compound <b>5</b>), DPTZ = 3,6-di­(pyridyl-2-yl)-1,2,4,5-tetrazine, and TBTA–(3-IP)₂ (compound <b>6</b>), 3-IP = 3-iodopyridine]. All of the compounds were characterized by structural, spectral, and thermal studies. Supramolecular structural analysis reveals that <b>1</b> forms a 2D supramolecular sheet structure by means of O–H···Br hydrogen bonding interactions and hydrated-<b>2</b> forms a 3D supramolecular structure through water mediated hydrogen bonding interactions and π··· interactions. The O–H···N/O¯···H–N⁺ hydrogen bonding interactions between acid and base molecules give rise to 1D supramolecular chain structure in <b>3</b> and supramolecular trimers in <b>4</b>, <b>5</b>, and <b>6</b>. Because of presence of charge assisted O^¯···H–N⁺ hydrogen bonds between acid–base molecules, <b>3</b> and <b>4</b> form hydrogen bonds with solvent water molecules, and also both <b>3</b> and <b>4</b> form 3D supramolecular structures using both hydrogen bonding and π··· interactions. In co-crystal <b>5</b>, solvent water molecules participate in crystallization in contrast to <b>6</b>, and it has been observed that <b>5</b> forms 3D supramolecular structure, while <b>6</b> forms 2D supramolecular structure using both hydrogen bonding and π··· interactions. An investigation of intermolecular closed contacts has been carried out by Hirshfeld surface analysis, and associated 2D fingerprint plots reveal the similarities and differences of TBTA molecules in these six crystal structures. Photoluminescence spectra of all the compounds have been studied, and they reveal that with change of polarity around TBTA luminescent intensity of the compounds has been modified. <i>I</i>–<i>V</i> measurement indicates that <b>3</b> shows semiconducting behavior, and the ITO/<b>3</b>/Al sandwich structure acts as a Schottky barrier diode. The device exhibits an excellent rectification ratio (19 at ±1 V) with an ideality factor of 2.96. The semiconducting behavior of <b>3</b> is attributed to the formation charge assisted hydrogen bonding interactions between acid and base molecules