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Synthesis, crystal structure and magnetic property of 30-membered decanuclear manganese metallacrown with N-cyclohexanoylsalicylhydrazide ligand
Journal Pre-proofs Synthesis, crystal structure and magnetic property of 30-membered decanuclear manganese metallacrown with N-cyclohexanoylsalicylhydrazide ligand Kangkai Du, Shi-Xiong Liu, Bizhou Lin PII: DOI: Reference:
S1387-7003(19)30809-3 https://doi.org/10.1016/j.inoche.2019.107606 INOCHE 107606
To appear in:
Inorganic Chemistry Communications
Received Date: Revised Date: Accepted Date:
8 August 2019 6 October 2019 11 October 2019
Please cite this article as: K. Du, S-X. Liu, B. Lin, Synthesis, crystal structure and magnetic property of 30membered decanuclear manganese metallacrown with N-cyclohexanoylsalicylhydrazide ligand, Inorganic Chemistry Communications (2019), doi: https://doi.org/10.1016/j.inoche.2019.107606
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© 2019 Published by Elsevier B.V.
Synthesis, crystal structure and magnetic property of 30-membered decanuclear manganese metallacrown with N-cyclohexanoylsalicylhydrazide ligand
Kangkai Du a,*, Shi-Xiong Liu b, Bizhou Lin a a)
College of Materials Science and Engineering, Huaqiao University, Xiamen 361021, China;
b)
Central Laboratory, Fuzhou University, Fuzhou 350002, China
----------------------------------* Corresponding author. Fax: +86-592-6162225. E-mail address: [email protected] (K. Du).
1
Abstract Pentadentate ligand, N-cyclohexanoylsalicylhydrazide (H3chxshz) (1), and its self-assembled 30-metallacrown-10, [Mn10(C14H15N2O3)10(CH3OH)10]·16CH3OH (2), have been synthesized. Ten manganese (III) ions and ten deprotonated ligands (chxshz3-) construct a 30-membered ring based on the M-N-N-M linkage in the novel decanuclear manganese(III) metallamacrocycle 2. The chiralities of Mn atoms in the diaza-bridged ring are in alternating and configurations. The magnetic property of the title 30-metallacrown-10 shows a weak antiferromagnetic exchange interaction with an observed eff of 14.93 B at 300 K.
Keywords: Metallamacrocycle; Metallacrown; Manganese complex; Crystal structure
Metallamacrocycles [1-5], such as metal wheels [5-7] and metallacrowns [8-16], are a dynamic research area in the field of supramolecular coordination chemistry due to their diverse molecular architectures, fascinating physicochemical properties and potential applications. Up to now there are three types of metallacrowns: with a [M-N-O]n core [6-8], with a [M-N-N]n core [9-14] and the others without [M-N-O]n or [M-N-N]n core [6-8]. Among them, the second metallacrowns with a [M-N-N]n core are called as diaza-bridged metallamacrocycles. Design of N-substituted salicylhydrazide ligand is crucial for preparing such metallacrowns. Many attempts have been done to control the different nuclear number of polynuclear compounds and metallacrowns [1,10,15,16]. It was revealed that the N-substituted group in the salicylhydrazide is always on the inner side of a 3n-membered ring in the known diaza-bridged metallomacrocycles and that the size of the N-substituted group in the salicylhydrazide is bigger, the member of the core ring is more. When the alkyl site of the N-substituted salicylhydrazide is replaced by isobutyryl, phenyl and cyclohexanoyl sites, hexanuclear, octanuclear, decanuclear and dodecanuclear diaza-bridged metallamacrocycles have been synthesized, respectively [13,17]. It means that the core ring size in the metallamacrocycles may result from the steric factor of the N-substituted groups [18-24]. Using the ligand
2
N-cyclohexanoylsalicylhydrazide, a dodecanuclear metallamacrocycle was synthesized by Lah’s group through the diffusion route [17]. The small molecule, benzene, is wrapped into the cavity by the slow diffusion reaction. Using the ligand N-phenylsalicylhydrazidate, a decanuclear metallamacrocycle have been synthesized by our group through the direct solution synthesis, rather than the evaporation diffusion [14]. As part of our efforts to control the metallacrown sizes through changing the ligands and their bond linkages, herein we report the synthesis and crystal structures of the pentadentate ligand N-hexahydrobenzoylsalicylhydrazide (H3chxshz, compound 1) and its diaza-bridged metallacrowns with 30-membered decanuclear manganeses [Mn10(C14H15N2O3)10(CH3OH)10]·16CH3OH (2).
Fig. 1
Intermolecular H-bonds in H3chxshz (1).
The ligand H3chxshz (1) was synthesized from the reaction of cyclohexanoyl chloride, salicylhydrazide and trithylamine in an ice-water bath (Experimental details see Supporting Information). Compound 1 crystallizes in monoclinic space group Cc with a = 10.111(6), b = 20.306(14), c = 7.013(4) Å, = 104.44(3), V = 1394.3(15) Å3 and Z = 4 (Table S1). In its structure (Fig. 1), there is a little twisting (6.19) about C7-O2-N1 for the benzene ring. The N1 and N2 are the p-π conjugation to double bond C7-O2 and C8-O3 respectively. The torsion angle of C7-N1-N2-C8 is 134.26(6), and N1-N2-C8-O3 is –2.4(3). There exists an intramolecular H-bond interaction, N1-H1B…O1. In its crystal structure, H3chxshz molecules are linked into a three-dimension interpenetrating network through intermolecular H-bonds, N2-H2A…O2# (the symmetry code: x, -y, z+1/2) and O1-H1A…O3# (the symmetry code: x-1/2,
3
-y+1/2, z-1/2). Interacting with manganese (III) ions, the deprotonated ligand (chxshz3-) was formed. The bond lengths of C2-O7 and C8-O3 are elongated and those of C7-N1 and C8-N2 are shortened. Compound 2 was collected through slow evaporation from the mixed solution containing H3chxshz and manganese(II) acetate in a molar ratio of 1:1 at room temperature (see Supporting Information). Powder X-ray diffraction (PXRD) and TG confirm the phase purity of the bulk product of 2 (Figs. S3 and S4). Single-crystal X-ray structural analysis reveals that compound 2 crystallizes in triclinic space group P-1 with a = 12.393(3), b = 21.022(5), c = 21.191(4) Å, = 107.717(11), = 105.484(9), = 92.618(11), V = 5019.3(19) Å3 and Z = 1 (Table S1). Its molecular structure is shown in Fig. 2. Ten manganese(III) ions and ten deprotonated chxshz3ligands construct a disc-shaped 30-membered core ring based on the Mn-N-N-Mn linkages. The title metallacrown has an inversion center with neighboring Mn...Mn interatomic distances from 4.872(2) to 4.906(2) Å and Mn...Mn...Mn angles of 129.22(4)-132.59(4).
Fig. 2
Molecular structure of decanuclear metallamacrocycle 30-membered ring in 2.
The peripheral diameter of the core ring in 2 is 20.44 Å, measured between the opposite carbon atoms (C29-C77, plus 0.77 Å for the van der Waals radii of C). The dimensions of the oval-shaped cavity are about 4.25 Å in internal diameter at the entrance, determined from the opposite carbon atoms in the N-substituted groups of chxshz3- (C34-C82), and about 11.31 Å at 4
its widest point, measured between the opposite Mn atoms. Each manganese atom is in a distorted octahedral MnN2O4 environment (Fig. 2). The bond distances for Mn-N (diazine, N1), Mn-O (phenolate or carbonyl) are in the range of 1.93-1.95, 1.85-1.88 and 1.90-1.94 Å, respectively. Those for Mn-N (diazine, N2) and Mn-O (CH3OH) are 2.22-2.25 and 2.22-2.34 Å, respectively. Several interatomic distances between the O atoms from the uncoordinated solvent molecules and the phenolate O atoms or the O atoms from the coordinated methanol are in the reasonable hydrogen bond range. All salicylyl planes of salicylhydrazide ligands are on the outside of the 30-membered core ring, and all N-substituted groups in the ligands are on the inner side of the ring. The flexibility around the N-N single bonds and the conformational adaptability of the pentadentate ligands chxshz3- is forcing all manganese(III) ions into a propeller configuration. The chiralities of the Mn3+ ions alternate in the and forms. The five methanol molecules coordinating to the Mn centers in the configuration are on one face of the disc-shaped decanuclear core ring, and the other five methanol molecules coordinating to the other Mn centers in the configuration are on the opposite side of the core ring. The two sides of each disc-shaped decanuclear core ring have opposite chiralities to each other. The molar effective magnetic moment (eff) of 2 is documented in Fig. 3. The magnetic moment for a ten isolated paramagnetic system with S = 2 is 15.18 B. The observed eff value at 300 K is 14.93 B, which is smaller than the expected spin-only value. It indicates that there is an antiferromagnetic coupling between the manganese(III) centers. With decreasing temperature, the magnetic moments decrease slightly to 12.86 B at 65 K, and then decrease rapidly and reach 3.96 B at 4.0 K. The antiferromagnetic coupling results in a negative Weiss constant = –35.8(4) K, derived from the fitting of Curie–Weiss law using the magnetic susceptibility (m) data with T > 23 K. This is similar to those reported for other metallacrowns or polynuclear compounds [14,15,19]. Structurally, the magnetic exchanging would likely propagate through pathways between the neighboring entities (J1) and those between the near-neighboring entities (J2). A simplified model was tested to quantitatively analyze the
5
magnetic behavior. A least-squares fit for all the data gives the parameters J1/k = -1.626(2) K, J2/k = -0.653(4) K, and the agreement factor F = [(obs − cal)2/obs] = 7.268 ×10-3, where k is the Boltzmann constant. The negative J values is a further evidence for the antiferromagnetic coupling between the paramagnetic Mn(III) ions. From the comparison with the derived absolute values of J1 and J2, one can conclude that the interactions between the neighboring centers dominate the others. The antiferromagnetic nature of the interaction may be originated from the overlap between the single occupied metal d orbitals through the bridging groups. 16
10
eff
14
8
eff ( B )
-1m
10
6
8
4
6
2
m-1 ( mol/emu )
12
4 0
50
100
150
200
250
300
0
T(K)
Fig. 3
Thermal variations of molar effective magnetic moment (eff) and inverse susceptibility
data (m-1) of compound 2, where open points denote observed results and solid lines for m-1 and eff represent the fitting results based on the Curie–Weiss law and on a simplified exchange fit as described in the text, respectively.
In summary, we synthesized an effective ligand H3chxshz to prepare a metallamacrocyclic manganese compound [Mn10(C14H15N2O3)10(CH3OH)10]·16CH3OH. The metal atoms in the diaza-bridged ring have alternating and forms and adopt a propeller configuration. All salicylyl planes of the ligands are on the outside of the ring, and all N-substituted groups are on the inner side. The magnetic property of the title 30-metallacrown-10 exhibits a weak antiferromagnetic exchange interaction.
Acknowledgments This project was supported by the Natural Science Foundation of Fujian Province, China
6
(2019H0013) and the Natural Science Foundation of Huaqiao University (07BS509).
Appendix A. Supplementary material Crystallographic data for the crystal structures reported in this paper can be obtained from the Cambridge Crystallographic Data Center, 12 Union Road, Cambridge CB21EZ, UK (fax: +44-1223-336-033; e-mail: [email protected] or http://www.ccdc.cam.ac.uk/) by referring to the CIF deposition code CCDC 642637 (1) and 642638 (2).
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Synthesis, crystal structure and magnetic property of 30-membered decanuclear manganese metallacrown with N-cyclohexanoylsalicylhydrazide ligand
Kangkai Du*, Shi-Xiong Liu, Bizhou Lin
10
Synthesis, crystal structure and magnetic property of 30-membered decanuclear manganese metallacrown with N-cyclohexanoylsalicylhydrazide ligand
Kangkai Du*, Shi-Xiong Liu, Bizhou Lin
Highlights
► Ten Mn(III) ions and ten ligands construct a 30-membered ring. ► Mn atoms in the diaza-bridged ring are in alternating and configurations. ► 30-metallacrown-10 shows a weak antiferromagnetic exchange interaction.
11
College of Materials Science and Engineering Huaqiao University Xiamen 361021 China October 5, 2019 Dear Editor, Ms. Ref. INOCHE_2019_733 Please consider this manuscript, entitled Synthesis, crystal structure and magnetic property of 30-membered decanuclear manganese metallacrown with N-cyclohexanoylsalicylhydrazide ligand for publication in Inorganic Chemistry Communications. We sincerely thank you and the reviewers for your kind comments on our manuscript. Responding to the comments made by you and the reviewers, some changes have been made in this revised manuscript. Please find our revised manuscript of the above paper. We state that the work is original, and has not been published previously, and that it is not under consideration for publication elsewhere. Its submission to the Journal was approved by all authors and our affiliation, Huaqiao University. If accepted, it will not be published elsewhere in the same form, in English or in any other language, without the written consent of the Publisher. The authors declare no competing financial interest.
Your sincerely,
Kangkai Du [email protected]
12
S1387-7003(19)30809-3 https://doi.org/10.1016/j.inoche.2019.107606 INOCHE 107606
To appear in:
Inorganic Chemistry Communications
Received Date: Revised Date: Accepted Date:
8 August 2019 6 October 2019 11 October 2019
Please cite this article as: K. Du, S-X. Liu, B. Lin, Synthesis, crystal structure and magnetic property of 30membered decanuclear manganese metallacrown with N-cyclohexanoylsalicylhydrazide ligand, Inorganic Chemistry Communications (2019), doi: https://doi.org/10.1016/j.inoche.2019.107606
This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
© 2019 Published by Elsevier B.V.
Synthesis, crystal structure and magnetic property of 30-membered decanuclear manganese metallacrown with N-cyclohexanoylsalicylhydrazide ligand
Kangkai Du a,*, Shi-Xiong Liu b, Bizhou Lin a a)
College of Materials Science and Engineering, Huaqiao University, Xiamen 361021, China;
b)
Central Laboratory, Fuzhou University, Fuzhou 350002, China
----------------------------------* Corresponding author. Fax: +86-592-6162225. E-mail address: [email protected] (K. Du).
1
Abstract Pentadentate ligand, N-cyclohexanoylsalicylhydrazide (H3chxshz) (1), and its self-assembled 30-metallacrown-10, [Mn10(C14H15N2O3)10(CH3OH)10]·16CH3OH (2), have been synthesized. Ten manganese (III) ions and ten deprotonated ligands (chxshz3-) construct a 30-membered ring based on the M-N-N-M linkage in the novel decanuclear manganese(III) metallamacrocycle 2. The chiralities of Mn atoms in the diaza-bridged ring are in alternating and configurations. The magnetic property of the title 30-metallacrown-10 shows a weak antiferromagnetic exchange interaction with an observed eff of 14.93 B at 300 K.
Keywords: Metallamacrocycle; Metallacrown; Manganese complex; Crystal structure
Metallamacrocycles [1-5], such as metal wheels [5-7] and metallacrowns [8-16], are a dynamic research area in the field of supramolecular coordination chemistry due to their diverse molecular architectures, fascinating physicochemical properties and potential applications. Up to now there are three types of metallacrowns: with a [M-N-O]n core [6-8], with a [M-N-N]n core [9-14] and the others without [M-N-O]n or [M-N-N]n core [6-8]. Among them, the second metallacrowns with a [M-N-N]n core are called as diaza-bridged metallamacrocycles. Design of N-substituted salicylhydrazide ligand is crucial for preparing such metallacrowns. Many attempts have been done to control the different nuclear number of polynuclear compounds and metallacrowns [1,10,15,16]. It was revealed that the N-substituted group in the salicylhydrazide is always on the inner side of a 3n-membered ring in the known diaza-bridged metallomacrocycles and that the size of the N-substituted group in the salicylhydrazide is bigger, the member of the core ring is more. When the alkyl site of the N-substituted salicylhydrazide is replaced by isobutyryl, phenyl and cyclohexanoyl sites, hexanuclear, octanuclear, decanuclear and dodecanuclear diaza-bridged metallamacrocycles have been synthesized, respectively [13,17]. It means that the core ring size in the metallamacrocycles may result from the steric factor of the N-substituted groups [18-24]. Using the ligand
2
N-cyclohexanoylsalicylhydrazide, a dodecanuclear metallamacrocycle was synthesized by Lah’s group through the diffusion route [17]. The small molecule, benzene, is wrapped into the cavity by the slow diffusion reaction. Using the ligand N-phenylsalicylhydrazidate, a decanuclear metallamacrocycle have been synthesized by our group through the direct solution synthesis, rather than the evaporation diffusion [14]. As part of our efforts to control the metallacrown sizes through changing the ligands and their bond linkages, herein we report the synthesis and crystal structures of the pentadentate ligand N-hexahydrobenzoylsalicylhydrazide (H3chxshz, compound 1) and its diaza-bridged metallacrowns with 30-membered decanuclear manganeses [Mn10(C14H15N2O3)10(CH3OH)10]·16CH3OH (2).
Fig. 1
Intermolecular H-bonds in H3chxshz (1).
The ligand H3chxshz (1) was synthesized from the reaction of cyclohexanoyl chloride, salicylhydrazide and trithylamine in an ice-water bath (Experimental details see Supporting Information). Compound 1 crystallizes in monoclinic space group Cc with a = 10.111(6), b = 20.306(14), c = 7.013(4) Å, = 104.44(3), V = 1394.3(15) Å3 and Z = 4 (Table S1). In its structure (Fig. 1), there is a little twisting (6.19) about C7-O2-N1 for the benzene ring. The N1 and N2 are the p-π conjugation to double bond C7-O2 and C8-O3 respectively. The torsion angle of C7-N1-N2-C8 is 134.26(6), and N1-N2-C8-O3 is –2.4(3). There exists an intramolecular H-bond interaction, N1-H1B…O1. In its crystal structure, H3chxshz molecules are linked into a three-dimension interpenetrating network through intermolecular H-bonds, N2-H2A…O2# (the symmetry code: x, -y, z+1/2) and O1-H1A…O3# (the symmetry code: x-1/2,
3
-y+1/2, z-1/2). Interacting with manganese (III) ions, the deprotonated ligand (chxshz3-) was formed. The bond lengths of C2-O7 and C8-O3 are elongated and those of C7-N1 and C8-N2 are shortened. Compound 2 was collected through slow evaporation from the mixed solution containing H3chxshz and manganese(II) acetate in a molar ratio of 1:1 at room temperature (see Supporting Information). Powder X-ray diffraction (PXRD) and TG confirm the phase purity of the bulk product of 2 (Figs. S3 and S4). Single-crystal X-ray structural analysis reveals that compound 2 crystallizes in triclinic space group P-1 with a = 12.393(3), b = 21.022(5), c = 21.191(4) Å, = 107.717(11), = 105.484(9), = 92.618(11), V = 5019.3(19) Å3 and Z = 1 (Table S1). Its molecular structure is shown in Fig. 2. Ten manganese(III) ions and ten deprotonated chxshz3ligands construct a disc-shaped 30-membered core ring based on the Mn-N-N-Mn linkages. The title metallacrown has an inversion center with neighboring Mn...Mn interatomic distances from 4.872(2) to 4.906(2) Å and Mn...Mn...Mn angles of 129.22(4)-132.59(4).
Fig. 2
Molecular structure of decanuclear metallamacrocycle 30-membered ring in 2.
The peripheral diameter of the core ring in 2 is 20.44 Å, measured between the opposite carbon atoms (C29-C77, plus 0.77 Å for the van der Waals radii of C). The dimensions of the oval-shaped cavity are about 4.25 Å in internal diameter at the entrance, determined from the opposite carbon atoms in the N-substituted groups of chxshz3- (C34-C82), and about 11.31 Å at 4
its widest point, measured between the opposite Mn atoms. Each manganese atom is in a distorted octahedral MnN2O4 environment (Fig. 2). The bond distances for Mn-N (diazine, N1), Mn-O (phenolate or carbonyl) are in the range of 1.93-1.95, 1.85-1.88 and 1.90-1.94 Å, respectively. Those for Mn-N (diazine, N2) and Mn-O (CH3OH) are 2.22-2.25 and 2.22-2.34 Å, respectively. Several interatomic distances between the O atoms from the uncoordinated solvent molecules and the phenolate O atoms or the O atoms from the coordinated methanol are in the reasonable hydrogen bond range. All salicylyl planes of salicylhydrazide ligands are on the outside of the 30-membered core ring, and all N-substituted groups in the ligands are on the inner side of the ring. The flexibility around the N-N single bonds and the conformational adaptability of the pentadentate ligands chxshz3- is forcing all manganese(III) ions into a propeller configuration. The chiralities of the Mn3+ ions alternate in the and forms. The five methanol molecules coordinating to the Mn centers in the configuration are on one face of the disc-shaped decanuclear core ring, and the other five methanol molecules coordinating to the other Mn centers in the configuration are on the opposite side of the core ring. The two sides of each disc-shaped decanuclear core ring have opposite chiralities to each other. The molar effective magnetic moment (eff) of 2 is documented in Fig. 3. The magnetic moment for a ten isolated paramagnetic system with S = 2 is 15.18 B. The observed eff value at 300 K is 14.93 B, which is smaller than the expected spin-only value. It indicates that there is an antiferromagnetic coupling between the manganese(III) centers. With decreasing temperature, the magnetic moments decrease slightly to 12.86 B at 65 K, and then decrease rapidly and reach 3.96 B at 4.0 K. The antiferromagnetic coupling results in a negative Weiss constant = –35.8(4) K, derived from the fitting of Curie–Weiss law using the magnetic susceptibility (m) data with T > 23 K. This is similar to those reported for other metallacrowns or polynuclear compounds [14,15,19]. Structurally, the magnetic exchanging would likely propagate through pathways between the neighboring entities (J1) and those between the near-neighboring entities (J2). A simplified model was tested to quantitatively analyze the
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magnetic behavior. A least-squares fit for all the data gives the parameters J1/k = -1.626(2) K, J2/k = -0.653(4) K, and the agreement factor F = [(obs − cal)2/obs] = 7.268 ×10-3, where k is the Boltzmann constant. The negative J values is a further evidence for the antiferromagnetic coupling between the paramagnetic Mn(III) ions. From the comparison with the derived absolute values of J1 and J2, one can conclude that the interactions between the neighboring centers dominate the others. The antiferromagnetic nature of the interaction may be originated from the overlap between the single occupied metal d orbitals through the bridging groups. 16
10
eff
14
8
eff ( B )
-1m
10
6
8
4
6
2
m-1 ( mol/emu )
12
4 0
50
100
150
200
250
300
0
T(K)
Fig. 3
Thermal variations of molar effective magnetic moment (eff) and inverse susceptibility
data (m-1) of compound 2, where open points denote observed results and solid lines for m-1 and eff represent the fitting results based on the Curie–Weiss law and on a simplified exchange fit as described in the text, respectively.
In summary, we synthesized an effective ligand H3chxshz to prepare a metallamacrocyclic manganese compound [Mn10(C14H15N2O3)10(CH3OH)10]·16CH3OH. The metal atoms in the diaza-bridged ring have alternating and forms and adopt a propeller configuration. All salicylyl planes of the ligands are on the outside of the ring, and all N-substituted groups are on the inner side. The magnetic property of the title 30-metallacrown-10 exhibits a weak antiferromagnetic exchange interaction.
Acknowledgments This project was supported by the Natural Science Foundation of Fujian Province, China
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(2019H0013) and the Natural Science Foundation of Huaqiao University (07BS509).
Appendix A. Supplementary material Crystallographic data for the crystal structures reported in this paper can be obtained from the Cambridge Crystallographic Data Center, 12 Union Road, Cambridge CB21EZ, UK (fax: +44-1223-336-033; e-mail: [email protected] or http://www.ccdc.cam.ac.uk/) by referring to the CIF deposition code CCDC 642637 (1) and 642638 (2).
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Synthesis, crystal structure and magnetic property of 30-membered decanuclear manganese metallacrown with N-cyclohexanoylsalicylhydrazide ligand
Kangkai Du*, Shi-Xiong Liu, Bizhou Lin
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Synthesis, crystal structure and magnetic property of 30-membered decanuclear manganese metallacrown with N-cyclohexanoylsalicylhydrazide ligand
Kangkai Du*, Shi-Xiong Liu, Bizhou Lin
Highlights
► Ten Mn(III) ions and ten ligands construct a 30-membered ring. ► Mn atoms in the diaza-bridged ring are in alternating and configurations. ► 30-metallacrown-10 shows a weak antiferromagnetic exchange interaction.
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College of Materials Science and Engineering Huaqiao University Xiamen 361021 China October 5, 2019 Dear Editor, Ms. Ref. INOCHE_2019_733 Please consider this manuscript, entitled Synthesis, crystal structure and magnetic property of 30-membered decanuclear manganese metallacrown with N-cyclohexanoylsalicylhydrazide ligand for publication in Inorganic Chemistry Communications. We sincerely thank you and the reviewers for your kind comments on our manuscript. Responding to the comments made by you and the reviewers, some changes have been made in this revised manuscript. Please find our revised manuscript of the above paper. We state that the work is original, and has not been published previously, and that it is not under consideration for publication elsewhere. Its submission to the Journal was approved by all authors and our affiliation, Huaqiao University. If accepted, it will not be published elsewhere in the same form, in English or in any other language, without the written consent of the Publisher. The authors declare no competing financial interest.
Your sincerely,
Kangkai Du [email protected]
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