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Syntheses, crystal structure and property of a heptanuclear cluster
Journal Pre-proofs Syntheses, Crystal Structure and Property of a Heptanuclear Cluster Ru-Xia Zhao, Jing Wang, Da-wei Jing, Hui-jing Zhang, Chao Feng, Guangyue Li PII: DOI: Reference:
S1387-7003(19)30866-4 https://doi.org/10.1016/j.inoche.2019.107597 INOCHE 107597
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Inorganic Chemistry Communications
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23 August 2019 24 September 2019 25 September 2019
Please cite this article as: R-X. Zhao, J. Wang, D-w. Jing, H-j. Zhang, C. Feng, G-y. Li, Syntheses, Crystal Structure and Property of a Heptanuclear Cluster, Inorganic Chemistry Communications (2019), doi: https:// doi.org/10.1016/j.inoche.2019.107597
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Syntheses, Crystal Structure and Property of a Heptanuclear Cluster Ru-Xia Zhao a*, Jing Wang a, Da-wei Jing a, Hui-jing Zhang a, Chao Feng b*, Guang-yue Li a a: Department of Pharmaceutical Engineering, Shandong Drug and Food Vocational College, Weihai 264200, People’s Republic of China b: School of Materials and Chemical Engineering, Bengbu University, Bengbu 233030, People’s Republic of China *
Corresponding authors. E-mail: [email protected] (R. X. Zhao), [email protected] (C. Feng)
Abstract: A new disc-like heptanuclear Ni(II) cluster [Ni7(emmp)6(μ3-N3)6]·(SiF6) (1) (H2emmp = 2-ethyoxy-6-methyliminomethyl-phenol), was synthesized and structurally determined by elemental analysis, IR, and X-ray single-crystal diffraction. Magnetic property of the complex has been investigated. The {Ni7} core displays dominant ferromagnetic interactions from the nature of the binding modes through by the EO-N3 and μ2-O. The latter molecule exhibits a unique planar core topology with 1:1.67 of the N3- : NiII ratio. Keywords: heptanuclear cluster; azido; crystal structure; magnetic property The rational design and synthesis of polynuclear complexes, aimed at understanding the structural and chemical factors that govern the exchange coupling between paramagnetic centres, are of continuing interest in biology, chemistry and physics [1–7]. In such molecules, controlling the interactions between metal ions provides a way to control the overall spin ground state of a complex. This consequently can have significant implications on its physical properties such as Single-Molecule Magnet (SMM) behaviour.[8] Polynuclear complexes with characteristic inner-bridged core structures are relatively well-known for exhibiting magnetic interactions that are ferro- or antiferromagnetic in nature without definite predictability.[8d,9-12] The synthesis of metal cluster compounds has always demanded the employment of polydentate bridging organic ligands, which serve to link the metal centers into a large polymetallic structure.[13] Indeed, several organic ligands have been used to date, from simple and flexible carboxylates[14,15] to more bulky and robust polyalcohols, oximes, and Schiff bases,[16,17] all leading to structural motifs with interesting physical and chemical properties. Our synthetic strategy focuses on employing chelating ligands which arrest the formation of coordination networks/sheets
and
form
well-isolated
complexes
while
maximizing
intramolecular
ferromagnetic interactions. 2-ethyoxy-6-methyliminomethyl-phenol (H2emmp) possessing two oxygen atoms of phenoxo, ethoxy groups and one nitrogen atoms of the methyliminomethyl group may provide the potential to construct unpredictable and interesting polymetallic clusters. On the other hand, the short bridges have extreme versatile bridging abilities in linking neighboring metal ions, thus strengthening the stability, and also are the key to acquiring predictable magnetic exchange along with the cooperation of appropriate external ligands.[18,19] There are many structurally related clusters with subtly short bridges that have been reported. We also had reported a series of oxo-bridged and azido bridged disc-like heptanuclear cluster[20-28]. Azido (N3-) ligand has been known for years as one of the most multitopic and versatile groups in
coordination chemistry, capable of bridging many metal centers and leading to beautiful structures with interesting magnetic properties where the type of magnetic interaction promoted depends highly on the bridging mode.[29-32] In the magnetism arena, it is now established that end-on (EO) bridging azido can promote strong ferromagnetic exchange interactions between the metal-spin carriers, thus leading to high-spin molecules, SMMs, and molecule-based magnets with long-range ferromagnetic ordering or spin-canting behaviors.[32] In addition to the magnetic properties, inorganic metal-azido compounds with a large N3-/Mn+ ratio could be potentially considered as high-energy materials due to their ability to form polymeric networks of single-bonded nitrogen with energy densities nearly three times greater than those of conventional highly explosive materials.[33] According to the above theoretical research and preliminary results of the study[20-28], direct reaction of 2-ethyoxy-6-methyliminomethyl-phenol with nickel salts in the presence of different anions (SiF6)2- was carried out, in order to further examine the effect of different anions on the structural assembly. The complex [Ni7(emmp)6(μ3-N3)6]·(SiF6) (1) can be obtained. The magnetic investigation shows ferromagnetic coupling between the metal ion (Insert here Fig. 1) Fig. 1 The structure of complex 1
The single-crystal X-ray diffraction analysis reveals that the complex 1 crystallizes in the trigonal space group R3, which asymmetric unit is shown in Fig. S1. As illustrated in Fig. 1, the complex consists of one wheel-like heptanuclear cluster, [Ni7(emmp)6(μ3-N3)6]2+, and one counter anion, (SiF6)2-. It can also be seen that the Ni2 atom located in the center of the structure bridged by six μ3-N3 groups, which are linked by six Ni atoms on the rim that represent the bottom segment of the formed disc-like structure. The coordination geometry of the central Ni2 ion can be described as a octahedron with bond lengths of 2.096(7) Å and bond angles in the range of 85.4 (3) – 94.6 (3) ° (cis-angles) and 180.0 ° (trans-angles). On the rim, each Ni1 atom adopts a NiN3O3 coordination configuration resulting from coordination of two emmp ligands and two μ3-N3 groups. The Ni1 atoms on the rim also formed distorted octahedral geometries as evidenced by the cisand trans-angle values ranging between 76.2 (3) and 106.6 (4) °, and 155.7 (3) and 163.5(4) °, respectively. Coordinated bond lengths around the rim Ni atoms are in the range of 1.984 (7) – 2.278(8) Å. Just as other {M7} clusters
[20-28]
, the magnetic interactions angles of Ni–N–Ni and
Ni–O–Ni are in the range of 94.5(3)°– 94.9(3)° and 109.1(3)°, respectively. And the adjacent Ni–Ni distances are 3.213–3.249 Å. As such, the emmp ligand, which displays a μ4:ƞ1:ƞ2:ƞ1 coordination mode (Scheme 1) lying alternately above and below the {Ni7} plane, is linked to two nickel in the compound of interest. All azido ligands in the complex are linear, herein, the N–N–N bond angles range from 176.6 (12) °. Though many heptanuclear clusters have been reported
[20-28]
, complex 1 also represent the
first heptanuclear nickel cluster, which emmp acts as peripheral tripodal ligand and azido acts as bridging ligand. The Ni7 units are well isolated by emmp ligands, ethoxy groups, and (SiF6)2– with
center distances between adjacent clusters of 15.016(3) Å in the ab plane and 12.7846(13) Å along the c direction (Fig. 2). The heptanuclear cluster constructed 3-D through abundant hydrogen bonds (C6-H6···F1, C9-H9B···F1). Compared with the compounds of our previous reports, a conclusion
can be drawn from the structural information different anion can cause slight differences in structure. And also, overall complex 1 consists of 1: 1.167 N3-: NiII ratio which makes this system potentially attractive for high-energy materials study. (Insert here Scheme 1) Scheme 1 Coordination mode of the ligand
(Insert here Fig. 2) Fig. 2 Relationship among clusters of 1
The magnetic susceptibilities of the complex was measured from crushed single crystalline samples and variable-temperature direct-current (dc) magnetic susceptibility data was collected in the temperature range of 2–300 K under an applied field of 1000 Oe. For complex 1, spin–orbital coupling of Ni (II) ions gives rise to a value of the χMT product of 12.19 cm3Kmol-1at room temperature (Fig. 3). This behavior suggests an orbital contribution of Ni (II) ions. For 1, this value is higher than the calculated spin-only value of 6.94 cm3Kmol-1 from seven non-interaction high-spin Ni(II) ions assuming g = 2.0.[21]The reason for the high χMT value at room temperature is that there exists orbital contribution in complex 1. Upon decreasing T, the χMT products of the complex gradually increase to maximum values of 34.10cm3Kmol-1 at 8 K, and then sharply fall to 24.9cm3Kmol-1 at 2 K. The sudden decrease of χMT is assigned to zero-field splitting in the ground state, Zeeman effects, or intercluster antiferromagnetic interactions at low temperatures. The increase of χMT with decreasing temperatures is indicative of strong ferromagnetic coupling between the metal centres which is evident even at room temperature since the χMT value is higher than the aforementioned theoretical value. From the experimental and theoretical data, it was concluded that an antiferromagnetic coupling should be expected for phenoxido-bridged Ni (II) complexes showing a Ni-O-Ni angle larger than 93-96° [34]. In the current compound, Ni-O-Ni shows values of 109.04°ˈwhich is above the previously mentioned crossover angle. Thus, we can deduce that the observed ferromagnetic coupling is induced by the EO-N3 bridges which tend to promote magnetic-orbital orthogonality due to Ni-N-Ni angle of 94.2°-98.7°, according to the reference [30, 32a, 35]. The temperature dependence of the reciprocal susceptibility χM-1 above 44 K follows the Curie–Weiss law [χ = C / (T - θ)] with Weiss and Curie constants of 27.19 K and 11.00 cm3Kmol-1 for the complex. (Fig. S2). The larger positive Weiss constants indicate an intramolecular II
ferromagnetic interaction between adjacent Ni ions of 1.
(Insert here Fig.3) Fig. 3 Plot of χM–T and χMT–T for 1
(Insert here Fig.4) Fig. 4 Plot of χ’’ -T and χ’’-T for 1
Further evidence of ferromagnetic coupling between Ni(II) ions was observed in the variable-field magnetization curves plotted in Fig. S3. At low fields from 0 to 10000 Oe, the magnetization of the complex sharply increases. Above 10000 Oe, the magnetization slowly increases but does not saturate at 50000 Oe. AC susceptibility measurements of the complex was carried out in the 2–10 K range at frequencies 100 Hz, 997 Hz (Fig. 4). No out-of-phase ac signals above 2 K indicate that the complex does not behave as a SMM. The IR spectral data of the complex 1 is shown in Fig. S4. There are indications that broad bands in the range of 3430 cm-1 and 3160 cm–1can be assigned to hydrogen bonds among intermolecular and intramolecular in the complex. The complex 1 showed a new strong characteristic stretching vibration at 2095 cm-1 attributed to the azido ligand, νas (N3) of the azido ligand in the range 2067-2076 cm-1[36,37], it exhibits red shift that may due to coordinate to the metal ions. It is significant that band at 1631 cm-1and 1219cm-1 is attributable to ν (C=N) and ν (C-N) of the emmp ligand that coordinated to the metal ions, respectively
[38,39]
. The results
–1
indicate that the methylamine exist in the ligand of emmp. The band at 1459 cm is assigned to ν(C-O) hydroxyl of the emmp ligand.[40] The IR attribution is consistent with the crystal structure determination. We have described the synthesis, structure, magnetic property and IR spectrum of the heptanuclear cluster that is coordinated with azido and emmp. The complex 1 represents the first heptanuclear nickel cluster, which emmp acts as peripheral ligand and favoring magnetic isolation of the clusters and azido acts as bridging ligand. And also, complex 1 consists of 1: 1.167 N3-: Ni II ratio which makes this system potentially attractive for high-energy materials study. Additionally, magnetic property study indicates that it strong ferromagnetic coupling between the nickel centres.
Acknowledgements This work was supported by the National Nature Science Foundation of China (No. 51569008, 21861014), Program of the Collaborative Innovation Center for Exploration of Hidden Nonferrous Metal Deposits and Development of New Materials in Guangxi (No.GXYSXTZX 2017-II-3), the National Science Foundation for Cultivation of Bengbu University (Grant No. 2018GJPY03)
and
Starting
Research
Fund
of
Bengbu
University
(Grant
No.
BBXY2018KYQD15).
Supplement material Crystallographic data for the structure of 1 in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publications CCDC 1879185. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: [email protected]. Electronic supplementary information (ESI) available: Experimental Section. The asymmetric unit of complex 1. The plot of χM–1 vs T of 1. The plots of M-H of 1. IR spectrum of 1.
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Fig. 1 The structure of complex 1 Fig. 2 Relationship among clusters of 1 Fig. 3 Plot of χM–T and χMT–T for 1 Fig. 4 Plot of χ’’ -T and χ’’-T for 1 Scheme 1 Coordination mode of the ligand
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Scheme 1
Graphical abstract
Highlights z
A new disc-like heptanuclear Ni(II) cluster [Ni7(emmp)6(μ3-N3)6]·(SiF6) was synthesized㸪 which is bridged by azido and phenoxido of H2emmp.
z
In the cluster, Ni-O-Ni shows values of 109.04°, while Ni-N-Ni angle is 94.2°-98.7°
z
The cluster displays ferromagnetic interaction between adjacent NiII ions, which is induced by the EO-N3 bridges
Conflict of interest statement We declare that we have no financial and personal relationships with other people or organizations that can inappropriately influence our work, there is no professional or other personal interest of any nature or kind in any product, service and/or company that could be construed as influencing the position presented in, or the review of, the manuscript entitled ’Syntheses, Crystal Structure and Property of a Heptanuclear Cluster’
S1387-7003(19)30866-4 https://doi.org/10.1016/j.inoche.2019.107597 INOCHE 107597
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Inorganic Chemistry Communications
Received Date: Revised Date: Accepted Date:
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Please cite this article as: R-X. Zhao, J. Wang, D-w. Jing, H-j. Zhang, C. Feng, G-y. Li, Syntheses, Crystal Structure and Property of a Heptanuclear Cluster, Inorganic Chemistry Communications (2019), doi: https:// doi.org/10.1016/j.inoche.2019.107597
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Syntheses, Crystal Structure and Property of a Heptanuclear Cluster Ru-Xia Zhao a*, Jing Wang a, Da-wei Jing a, Hui-jing Zhang a, Chao Feng b*, Guang-yue Li a a: Department of Pharmaceutical Engineering, Shandong Drug and Food Vocational College, Weihai 264200, People’s Republic of China b: School of Materials and Chemical Engineering, Bengbu University, Bengbu 233030, People’s Republic of China *
Corresponding authors. E-mail: [email protected] (R. X. Zhao), [email protected] (C. Feng)
Abstract: A new disc-like heptanuclear Ni(II) cluster [Ni7(emmp)6(μ3-N3)6]·(SiF6) (1) (H2emmp = 2-ethyoxy-6-methyliminomethyl-phenol), was synthesized and structurally determined by elemental analysis, IR, and X-ray single-crystal diffraction. Magnetic property of the complex has been investigated. The {Ni7} core displays dominant ferromagnetic interactions from the nature of the binding modes through by the EO-N3 and μ2-O. The latter molecule exhibits a unique planar core topology with 1:1.67 of the N3- : NiII ratio. Keywords: heptanuclear cluster; azido; crystal structure; magnetic property The rational design and synthesis of polynuclear complexes, aimed at understanding the structural and chemical factors that govern the exchange coupling between paramagnetic centres, are of continuing interest in biology, chemistry and physics [1–7]. In such molecules, controlling the interactions between metal ions provides a way to control the overall spin ground state of a complex. This consequently can have significant implications on its physical properties such as Single-Molecule Magnet (SMM) behaviour.[8] Polynuclear complexes with characteristic inner-bridged core structures are relatively well-known for exhibiting magnetic interactions that are ferro- or antiferromagnetic in nature without definite predictability.[8d,9-12] The synthesis of metal cluster compounds has always demanded the employment of polydentate bridging organic ligands, which serve to link the metal centers into a large polymetallic structure.[13] Indeed, several organic ligands have been used to date, from simple and flexible carboxylates[14,15] to more bulky and robust polyalcohols, oximes, and Schiff bases,[16,17] all leading to structural motifs with interesting physical and chemical properties. Our synthetic strategy focuses on employing chelating ligands which arrest the formation of coordination networks/sheets
and
form
well-isolated
complexes
while
maximizing
intramolecular
ferromagnetic interactions. 2-ethyoxy-6-methyliminomethyl-phenol (H2emmp) possessing two oxygen atoms of phenoxo, ethoxy groups and one nitrogen atoms of the methyliminomethyl group may provide the potential to construct unpredictable and interesting polymetallic clusters. On the other hand, the short bridges have extreme versatile bridging abilities in linking neighboring metal ions, thus strengthening the stability, and also are the key to acquiring predictable magnetic exchange along with the cooperation of appropriate external ligands.[18,19] There are many structurally related clusters with subtly short bridges that have been reported. We also had reported a series of oxo-bridged and azido bridged disc-like heptanuclear cluster[20-28]. Azido (N3-) ligand has been known for years as one of the most multitopic and versatile groups in
coordination chemistry, capable of bridging many metal centers and leading to beautiful structures with interesting magnetic properties where the type of magnetic interaction promoted depends highly on the bridging mode.[29-32] In the magnetism arena, it is now established that end-on (EO) bridging azido can promote strong ferromagnetic exchange interactions between the metal-spin carriers, thus leading to high-spin molecules, SMMs, and molecule-based magnets with long-range ferromagnetic ordering or spin-canting behaviors.[32] In addition to the magnetic properties, inorganic metal-azido compounds with a large N3-/Mn+ ratio could be potentially considered as high-energy materials due to their ability to form polymeric networks of single-bonded nitrogen with energy densities nearly three times greater than those of conventional highly explosive materials.[33] According to the above theoretical research and preliminary results of the study[20-28], direct reaction of 2-ethyoxy-6-methyliminomethyl-phenol with nickel salts in the presence of different anions (SiF6)2- was carried out, in order to further examine the effect of different anions on the structural assembly. The complex [Ni7(emmp)6(μ3-N3)6]·(SiF6) (1) can be obtained. The magnetic investigation shows ferromagnetic coupling between the metal ion (Insert here Fig. 1) Fig. 1 The structure of complex 1
The single-crystal X-ray diffraction analysis reveals that the complex 1 crystallizes in the trigonal space group R3, which asymmetric unit is shown in Fig. S1. As illustrated in Fig. 1, the complex consists of one wheel-like heptanuclear cluster, [Ni7(emmp)6(μ3-N3)6]2+, and one counter anion, (SiF6)2-. It can also be seen that the Ni2 atom located in the center of the structure bridged by six μ3-N3 groups, which are linked by six Ni atoms on the rim that represent the bottom segment of the formed disc-like structure. The coordination geometry of the central Ni2 ion can be described as a octahedron with bond lengths of 2.096(7) Å and bond angles in the range of 85.4 (3) – 94.6 (3) ° (cis-angles) and 180.0 ° (trans-angles). On the rim, each Ni1 atom adopts a NiN3O3 coordination configuration resulting from coordination of two emmp ligands and two μ3-N3 groups. The Ni1 atoms on the rim also formed distorted octahedral geometries as evidenced by the cisand trans-angle values ranging between 76.2 (3) and 106.6 (4) °, and 155.7 (3) and 163.5(4) °, respectively. Coordinated bond lengths around the rim Ni atoms are in the range of 1.984 (7) – 2.278(8) Å. Just as other {M7} clusters
[20-28]
, the magnetic interactions angles of Ni–N–Ni and
Ni–O–Ni are in the range of 94.5(3)°– 94.9(3)° and 109.1(3)°, respectively. And the adjacent Ni–Ni distances are 3.213–3.249 Å. As such, the emmp ligand, which displays a μ4:ƞ1:ƞ2:ƞ1 coordination mode (Scheme 1) lying alternately above and below the {Ni7} plane, is linked to two nickel in the compound of interest. All azido ligands in the complex are linear, herein, the N–N–N bond angles range from 176.6 (12) °. Though many heptanuclear clusters have been reported
[20-28]
, complex 1 also represent the
first heptanuclear nickel cluster, which emmp acts as peripheral tripodal ligand and azido acts as bridging ligand. The Ni7 units are well isolated by emmp ligands, ethoxy groups, and (SiF6)2– with
center distances between adjacent clusters of 15.016(3) Å in the ab plane and 12.7846(13) Å along the c direction (Fig. 2). The heptanuclear cluster constructed 3-D through abundant hydrogen bonds (C6-H6···F1, C9-H9B···F1). Compared with the compounds of our previous reports, a conclusion
can be drawn from the structural information different anion can cause slight differences in structure. And also, overall complex 1 consists of 1: 1.167 N3-: NiII ratio which makes this system potentially attractive for high-energy materials study. (Insert here Scheme 1) Scheme 1 Coordination mode of the ligand
(Insert here Fig. 2) Fig. 2 Relationship among clusters of 1
The magnetic susceptibilities of the complex was measured from crushed single crystalline samples and variable-temperature direct-current (dc) magnetic susceptibility data was collected in the temperature range of 2–300 K under an applied field of 1000 Oe. For complex 1, spin–orbital coupling of Ni (II) ions gives rise to a value of the χMT product of 12.19 cm3Kmol-1at room temperature (Fig. 3). This behavior suggests an orbital contribution of Ni (II) ions. For 1, this value is higher than the calculated spin-only value of 6.94 cm3Kmol-1 from seven non-interaction high-spin Ni(II) ions assuming g = 2.0.[21]The reason for the high χMT value at room temperature is that there exists orbital contribution in complex 1. Upon decreasing T, the χMT products of the complex gradually increase to maximum values of 34.10cm3Kmol-1 at 8 K, and then sharply fall to 24.9cm3Kmol-1 at 2 K. The sudden decrease of χMT is assigned to zero-field splitting in the ground state, Zeeman effects, or intercluster antiferromagnetic interactions at low temperatures. The increase of χMT with decreasing temperatures is indicative of strong ferromagnetic coupling between the metal centres which is evident even at room temperature since the χMT value is higher than the aforementioned theoretical value. From the experimental and theoretical data, it was concluded that an antiferromagnetic coupling should be expected for phenoxido-bridged Ni (II) complexes showing a Ni-O-Ni angle larger than 93-96° [34]. In the current compound, Ni-O-Ni shows values of 109.04°ˈwhich is above the previously mentioned crossover angle. Thus, we can deduce that the observed ferromagnetic coupling is induced by the EO-N3 bridges which tend to promote magnetic-orbital orthogonality due to Ni-N-Ni angle of 94.2°-98.7°, according to the reference [30, 32a, 35]. The temperature dependence of the reciprocal susceptibility χM-1 above 44 K follows the Curie–Weiss law [χ = C / (T - θ)] with Weiss and Curie constants of 27.19 K and 11.00 cm3Kmol-1 for the complex. (Fig. S2). The larger positive Weiss constants indicate an intramolecular II
ferromagnetic interaction between adjacent Ni ions of 1.
(Insert here Fig.3) Fig. 3 Plot of χM–T and χMT–T for 1
(Insert here Fig.4) Fig. 4 Plot of χ’’ -T and χ’’-T for 1
Further evidence of ferromagnetic coupling between Ni(II) ions was observed in the variable-field magnetization curves plotted in Fig. S3. At low fields from 0 to 10000 Oe, the magnetization of the complex sharply increases. Above 10000 Oe, the magnetization slowly increases but does not saturate at 50000 Oe. AC susceptibility measurements of the complex was carried out in the 2–10 K range at frequencies 100 Hz, 997 Hz (Fig. 4). No out-of-phase ac signals above 2 K indicate that the complex does not behave as a SMM. The IR spectral data of the complex 1 is shown in Fig. S4. There are indications that broad bands in the range of 3430 cm-1 and 3160 cm–1can be assigned to hydrogen bonds among intermolecular and intramolecular in the complex. The complex 1 showed a new strong characteristic stretching vibration at 2095 cm-1 attributed to the azido ligand, νas (N3) of the azido ligand in the range 2067-2076 cm-1[36,37], it exhibits red shift that may due to coordinate to the metal ions. It is significant that band at 1631 cm-1and 1219cm-1 is attributable to ν (C=N) and ν (C-N) of the emmp ligand that coordinated to the metal ions, respectively
[38,39]
. The results
–1
indicate that the methylamine exist in the ligand of emmp. The band at 1459 cm is assigned to ν(C-O) hydroxyl of the emmp ligand.[40] The IR attribution is consistent with the crystal structure determination. We have described the synthesis, structure, magnetic property and IR spectrum of the heptanuclear cluster that is coordinated with azido and emmp. The complex 1 represents the first heptanuclear nickel cluster, which emmp acts as peripheral ligand and favoring magnetic isolation of the clusters and azido acts as bridging ligand. And also, complex 1 consists of 1: 1.167 N3-: Ni II ratio which makes this system potentially attractive for high-energy materials study. Additionally, magnetic property study indicates that it strong ferromagnetic coupling between the nickel centres.
Acknowledgements This work was supported by the National Nature Science Foundation of China (No. 51569008, 21861014), Program of the Collaborative Innovation Center for Exploration of Hidden Nonferrous Metal Deposits and Development of New Materials in Guangxi (No.GXYSXTZX 2017-II-3), the National Science Foundation for Cultivation of Bengbu University (Grant No. 2018GJPY03)
and
Starting
Research
Fund
of
Bengbu
University
(Grant
No.
BBXY2018KYQD15).
Supplement material Crystallographic data for the structure of 1 in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publications CCDC 1879185. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: [email protected]. Electronic supplementary information (ESI) available: Experimental Section. The asymmetric unit of complex 1. The plot of χM–1 vs T of 1. The plots of M-H of 1. IR spectrum of 1.
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Fig. 1 The structure of complex 1 Fig. 2 Relationship among clusters of 1 Fig. 3 Plot of χM–T and χMT–T for 1 Fig. 4 Plot of χ’’ -T and χ’’-T for 1 Scheme 1 Coordination mode of the ligand
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Scheme 1
Graphical abstract
Highlights z
A new disc-like heptanuclear Ni(II) cluster [Ni7(emmp)6(μ3-N3)6]·(SiF6) was synthesized㸪 which is bridged by azido and phenoxido of H2emmp.
z
In the cluster, Ni-O-Ni shows values of 109.04°, while Ni-N-Ni angle is 94.2°-98.7°
z
The cluster displays ferromagnetic interaction between adjacent NiII ions, which is induced by the EO-N3 bridges
Conflict of interest statement We declare that we have no financial and personal relationships with other people or organizations that can inappropriately influence our work, there is no professional or other personal interest of any nature or kind in any product, service and/or company that could be construed as influencing the position presented in, or the review of, the manuscript entitled ’Syntheses, Crystal Structure and Property of a Heptanuclear Cluster’