Synthesis and structure of aquamethanol-2′,2‴-(2,6-pyridin-diyldiethylidene)-dioxamohydrazidocobalt(II) perchlorate

Role of Spin State and Ligand Charge in Coordination Patterns in Complexes of 2,6-Diacetylpyridinebis(semioxamazide) with 3d-Block Metal Ions: A Density Functional Theory Study

“…This trend has been observed for all investigated [M(H n dapsox)(H 2 O) 2 ] q complexes with other metals; see Table S1 in the Supporting Information. It is noteworthy that the geometries of the calculated structures of isomer I are in excellent agreement with those of similar structures characterized by X-ray. − Selected bond lengths and valence angles are collected and compared in Table S2 in the Supporting Information for corresponding structures, while the superposition of some of the crystal structures − and structures computed at the LDA level are presented in Figure . This figure shows the large coherence between the optimized and X-ray structures, which is the confirmation that LDA tends to give good geometries for coordination compounds. ,− …”

“…30,33 Whenever a different ground state is possible, high spin is always observed. In order to elucidate the factors that govern this structural preference, we performed DFT calculations for all of the above-mentioned isomers (I−XII) of [M(H n dapsox)(H 2 O) 2 ] q to examine their relative stability (see Figure 2), although some of them cannot be experimentally achieved.…”

“…Even though there is the likelihood of formation of each isomer, it has been experimentally confirmed that the H n dapsox ligand always forms isomer I (PBPY-7) complexes with Mn II , 28 Fe III , 31,32 Fe II , 29 and Co II . 30,33 Whenever a different ground state is possible, high spin is always observed. In order to elucidate the factors that govern this structural preference, we performed DFT calculations for all of the above-mentioned isomers (I−XII) of [M(H n dapsox)(H 2 O) 2 ] q to examine their relative stability (see Figure 2), although some of them cannot be experimentally achieved.…”

“…The H 2 dapsox ligand studied here has 11 potential ligator atoms (see Figure ), some of which are mutually exclusive. This, together with the flexibility of both side chains attached to the pyridine ring, creates quite a diversified stereochemistry with respect to the possible coordination modes, which could be summarized as follows: isomer I corresponds to the PBPY-7 X-ray-determined structures of the investigated complexes (vide supra), − while isomers II and III might be quoted as rotamers of isomer I .…”

Role of Spin State and Ligand Charge in Coordination Patterns in Complexes of 2,6-Diacetylpyridinebis(semioxamazide) with 3d-Block Metal Ions: A Density Functional Theory Study

“…This trend has been observed for all investigated [M(H n dapsox)(H 2 O) 2 ] q complexes with other metals; see Table S1 in the Supporting Information. It is noteworthy that the geometries of the calculated structures of isomer I are in excellent agreement with those of similar structures characterized by X-ray. − Selected bond lengths and valence angles are collected and compared in Table S2 in the Supporting Information for corresponding structures, while the superposition of some of the crystal structures − and structures computed at the LDA level are presented in Figure . This figure shows the large coherence between the optimized and X-ray structures, which is the confirmation that LDA tends to give good geometries for coordination compounds. ,− …”

“…30,33 Whenever a different ground state is possible, high spin is always observed. In order to elucidate the factors that govern this structural preference, we performed DFT calculations for all of the above-mentioned isomers (I−XII) of [M(H n dapsox)(H 2 O) 2 ] q to examine their relative stability (see Figure 2), although some of them cannot be experimentally achieved.…”

“…Even though there is the likelihood of formation of each isomer, it has been experimentally confirmed that the H n dapsox ligand always forms isomer I (PBPY-7) complexes with Mn II , 28 Fe III , 31,32 Fe II , 29 and Co II . 30,33 Whenever a different ground state is possible, high spin is always observed. In order to elucidate the factors that govern this structural preference, we performed DFT calculations for all of the above-mentioned isomers (I−XII) of [M(H n dapsox)(H 2 O) 2 ] q to examine their relative stability (see Figure 2), although some of them cannot be experimentally achieved.…”

“…The H 2 dapsox ligand studied here has 11 potential ligator atoms (see Figure ), some of which are mutually exclusive. This, together with the flexibility of both side chains attached to the pyridine ring, creates quite a diversified stereochemistry with respect to the possible coordination modes, which could be summarized as follows: isomer I corresponds to the PBPY-7 X-ray-determined structures of the investigated complexes (vide supra), − while isomers II and III might be quoted as rotamers of isomer I .…”

Cobalt(II), Zinc(II), Iron(III), and Copper(II) Complexes Bearing Positively Charged Quaternary Ammonium Functionalities: Synthesis, Characterization, Electrochemical Behavior, and SOD Activity

“…In general, the ligand H 2 dapsox differs from H 2 L 2+ in the number of potential donor atoms (11 vs. 7), although in both cases some of them are mutually exclusive. The H 2 dapsox is able to form different in‐plane combinations of the five‐ and six‐membered chelation rings upon coordination to metal ions either as pentadentate or tetradentate ligand,, while a pentadentate coordination of H 2 L 2+ or L to metal ion can only be achieved by formation of four fused five‐membered chelation rings. Therefore, the geometrical isomerism of metal complexes with H 2 dapsox or its deprotonated forms is much more intricate compared to that of metal complexes with H 2 L 2+ or L .…”

Role of Spin State and Ligand Charge in Coordination Patterns in Complexes of 2,6-Diacetylpyridinebis(semioxamazide) with 3d-Block Metal Ions: A Density Functional Theory Study

“…This trend has been observed for all investigated [M(H n dapsox)(H 2 O) 2 ] q complexes with other metals; see Table S1 in the Supporting Information. It is noteworthy that the geometries of the calculated structures of isomer I are in excellent agreement with those of similar structures characterized by X-ray. − Selected bond lengths and valence angles are collected and compared in Table S2 in the Supporting Information for corresponding structures, while the superposition of some of the crystal structures − and structures computed at the LDA level are presented in Figure . This figure shows the large coherence between the optimized and X-ray structures, which is the confirmation that LDA tends to give good geometries for coordination compounds. ,− …”

“…30,33 Whenever a different ground state is possible, high spin is always observed. In order to elucidate the factors that govern this structural preference, we performed DFT calculations for all of the above-mentioned isomers (I−XII) of [M(H n dapsox)(H 2 O) 2 ] q to examine their relative stability (see Figure 2), although some of them cannot be experimentally achieved.…”

“…Even though there is the likelihood of formation of each isomer, it has been experimentally confirmed that the H n dapsox ligand always forms isomer I (PBPY-7) complexes with Mn II , 28 Fe III , 31,32 Fe II , 29 and Co II . 30,33 Whenever a different ground state is possible, high spin is always observed. In order to elucidate the factors that govern this structural preference, we performed DFT calculations for all of the above-mentioned isomers (I−XII) of [M(H n dapsox)(H 2 O) 2 ] q to examine their relative stability (see Figure 2), although some of them cannot be experimentally achieved.…”

“…The H 2 dapsox ligand studied here has 11 potential ligator atoms (see Figure ), some of which are mutually exclusive. This, together with the flexibility of both side chains attached to the pyridine ring, creates quite a diversified stereochemistry with respect to the possible coordination modes, which could be summarized as follows: isomer I corresponds to the PBPY-7 X-ray-determined structures of the investigated complexes (vide supra), − while isomers II and III might be quoted as rotamers of isomer I .…”

Cobalt(II), Zinc(II), Iron(III), and Copper(II) Complexes Bearing Positively Charged Quaternary Ammonium Functionalities: Synthesis, Characterization, Electrochemical Behavior, and SOD Activity

“…In general, the ligand H 2 dapsox differs from H 2 L 2+ in the number of potential donor atoms (11 vs. 7), although in both cases some of them are mutually exclusive. The H 2 dapsox is able to form different in‐plane combinations of the five‐ and six‐membered chelation rings upon coordination to metal ions either as pentadentate or tetradentate ligand,, while a pentadentate coordination of H 2 L 2+ or L to metal ion can only be achieved by formation of four fused five‐membered chelation rings. Therefore, the geometrical isomerism of metal complexes with H 2 dapsox or its deprotonated forms is much more intricate compared to that of metal complexes with H 2 L 2+ or L .…”

Role of Spin State and Ligand Charge in Coordination Patterns in Complexes of 2,6-Diacetylpyridinebis(semioxamazide) with 3d-Block Metal Ions: A Density Functional Theory Study

“…This trend has been observed for all investigated [M(H n dapsox)(H 2 O) 2 ] q complexes with other metals; see Table S1 in the Supporting Information. It is noteworthy that the geometries of the calculated structures of isomer I are in excellent agreement with those of similar structures characterized by X-ray. − Selected bond lengths and valence angles are collected and compared in Table S2 in the Supporting Information for corresponding structures, while the superposition of some of the crystal structures − and structures computed at the LDA level are presented in Figure . This figure shows the large coherence between the optimized and X-ray structures, which is the confirmation that LDA tends to give good geometries for coordination compounds. ,− …”

“…30,33 Whenever a different ground state is possible, high spin is always observed. In order to elucidate the factors that govern this structural preference, we performed DFT calculations for all of the above-mentioned isomers (I−XII) of [M(H n dapsox)(H 2 O) 2 ] q to examine their relative stability (see Figure 2), although some of them cannot be experimentally achieved.…”

“…Even though there is the likelihood of formation of each isomer, it has been experimentally confirmed that the H n dapsox ligand always forms isomer I (PBPY-7) complexes with Mn II , 28 Fe III , 31,32 Fe II , 29 and Co II . 30,33 Whenever a different ground state is possible, high spin is always observed. In order to elucidate the factors that govern this structural preference, we performed DFT calculations for all of the above-mentioned isomers (I−XII) of [M(H n dapsox)(H 2 O) 2 ] q to examine their relative stability (see Figure 2), although some of them cannot be experimentally achieved.…”

“…The H 2 dapsox ligand studied here has 11 potential ligator atoms (see Figure ), some of which are mutually exclusive. This, together with the flexibility of both side chains attached to the pyridine ring, creates quite a diversified stereochemistry with respect to the possible coordination modes, which could be summarized as follows: isomer I corresponds to the PBPY-7 X-ray-determined structures of the investigated complexes (vide supra), − while isomers II and III might be quoted as rotamers of isomer I .…”

Cobalt(II), Zinc(II), Iron(III), and Copper(II) Complexes Bearing Positively Charged Quaternary Ammonium Functionalities: Synthesis, Characterization, Electrochemical Behavior, and SOD Activity

“…In general, the ligand H 2 dapsox differs from H 2 L 2+ in the number of potential donor atoms (11 vs. 7), although in both cases some of them are mutually exclusive. The H 2 dapsox is able to form different in‐plane combinations of the five‐ and six‐membered chelation rings upon coordination to metal ions either as pentadentate or tetradentate ligand,, while a pentadentate coordination of H 2 L 2+ or L to metal ion can only be achieved by formation of four fused five‐membered chelation rings. Therefore, the geometrical isomerism of metal complexes with H 2 dapsox or its deprotonated forms is much more intricate compared to that of metal complexes with H 2 L 2+ or L .…”