![Page 1: A 3D Co framework with alternating vertex- and edge ... · 1 Electronic Supplementary Information A 3D CoII framework with alternating vertex- and edge-sharing Δ-ribbon showing a](https://reader033.vdocuments.pub/reader033/viewer/2022060518/604c689953122853e0128f3a/html5/thumbnails/1.jpg)
1
Electronic Supplementary Information
A 3D CoII framework with alternating vertex- and edge-sharing Δ-ribbon showing a two-step
field-induced metamagnetic transition
En-Cui Yang*, Zhong-Yi Liu, Xiao-Yun Wu, and Xiao-Jun Zhao*
Synthesis of 1: A mixture containing CoCl2·6H2O (47.6 mg, 0.2 mmol), 1,2,3-benzenetricarboxylic acid (42.0
mg, 0.2 mmol), and 5-amino-1H-tetrazole (20.6 mg, 0.2 mmol) was dissolved in doubly deionized water (12.0
mL), and the initial pH value of the mixture was adjusted to ca. 4.0 by aqueous ammonia. The mixture was then
transferred into a parr Teflon-lined stainless steel vessel (23.0 mL) and heated to 200 oC for 24 h under
autogenous pressure. After the mixture was cooled to room temperature, red block-shaped crystals suitable for
X-ray analysis were generated directly, washed with ethanol and dried in air. Yield: 48.9% based on CoII salt.
Calc. for C17H19Co3.5N5O13.5 1: C 28.53, H 2.68, N 9.79%. Found: C 28.51, H 2.72, N 9.75%. IR (KBr, cm–1):
3476(br), 3367(w), 3072(w), 1606(s), 1562(s), 1480(w), 1454(w), 1412(s), 1391(s), 1359(s), 1268(w), 1157(w),
1081(w), 888(w), 749(m), 711(m), 653(w), 533(w), 416(w).
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
![Page 2: A 3D Co framework with alternating vertex- and edge ... · 1 Electronic Supplementary Information A 3D CoII framework with alternating vertex- and edge-sharing Δ-ribbon showing a](https://reader033.vdocuments.pub/reader033/viewer/2022060518/604c689953122853e0128f3a/html5/thumbnails/2.jpg)
2
Fig. S1. TG curve for 1.
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
![Page 3: A 3D Co framework with alternating vertex- and edge ... · 1 Electronic Supplementary Information A 3D CoII framework with alternating vertex- and edge-sharing Δ-ribbon showing a](https://reader033.vdocuments.pub/reader033/viewer/2022060518/604c689953122853e0128f3a/html5/thumbnails/3.jpg)
3
Fig. S2. Simulated and experimental X-ray powder diffraction patterns for 1.
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
![Page 4: A 3D Co framework with alternating vertex- and edge ... · 1 Electronic Supplementary Information A 3D CoII framework with alternating vertex- and edge-sharing Δ-ribbon showing a](https://reader033.vdocuments.pub/reader033/viewer/2022060518/604c689953122853e0128f3a/html5/thumbnails/4.jpg)
4
Table S1. Selected bond lengths and angles in 1 (Å, º).
Co(1)–O(1)#1 2.018(3) Co(1)–O(10) 2.043(3)
Co(1)–O(11) 2.066(3) Co(1)–O(3)#2 2.105(3)
Co(1)–N(1) 2.132(3) Co(1)–O(8)#3 2.288(3)
Co(2)–O(10)#1 2.083(3) Co(2)–O(4)#2 2.099(3)
Co(2)–O(10) 2.107(3) Co(2)–N(2)#1 2.132(3)
Co(2)–O(9) 2.158(3) Co(2)–O(2) 2.176(3)
Co(3)–N(3)#4 2.045(3) Co(3)–O(9) 2.122(3)
Co(3)–O(7)#5 2.116(3) Co(4)–O(6) 2.164(3)
Co(4)–O(9) 2.061(3) Co(4)–O(8)#3 2.096(3)
Co(4)–O(3)#2 2.127(3) Co(4)–N(4)#4 2.135(3)
Co(4)–O(5) 2.148(3)
O(1)#1–Co(1)–O(10) 89.01(12) O(1)#1–Co(1)–O(11) 88.41(14)
O(10)–Co(1)–O(11) 171.91(15) O(1)#1–Co(1)–O(3)#2 172.86(12)
O(10)–Co(1)–O(3)#2 94.72(10) O(11)–Co(1)–O(3)#2 87.07(13)
O(1)#1–Co(1)–N(1) 95.58(14) O(10)–Co(1)–N(1) 92.84(11)
O(11)–Co(1)–N(1) 95.04(16) O(3)#2–Co(1)–N(1) 90.31(12)
O(1)#1–Co(1)–O(8)#3 96.05(12) O(10)–Co(1)–O(8)#3 86.68(10)
O(11)–Co(1)–O(8)#3 85.97(15) O(3)#2–Co(1)–O(8)#3 78.13(10)
N(1)–Co(1)–O(8)#3 168.34(12) O(10)#1–Co(2)–O(4)#2 98.15(11)
O(10)#1–Co(2)–O(10) 80.73(11) O(4)#2–Co(2)–O(10) 92.43(11)
O(10)#1–Co(2)–N(2)#1 83.85(11) O(4)#2–Co(2)–N(2)#1 176.47(13)
O(10)–Co(2)–N(2)#1 90.75(11) O(10)#1–Co(2)–O(9) 165.43(10)
O(4)#2–Co(2)–O(9) 92.78(11) O(10)–Co(2)–O(9) 89.25(10)
N(2)#1–Co(2)–O(9) 85.75(11) O(10)#1–Co(2)–O(2) 93.56(10)
O(4)#2–Co(2)–O(2) 83.79(11) O(10)–Co(2)–O(2) 172.67(11)
N(2)#1–Co(2)–O(2) 93.21(12) O(9)–Co(2)–O(2) 97.19(11)
N(3)#4–Co(3)–N(3)#1 180.0 N(3)#4–Co(3)–O(7)#5 92.03(13)
N(3)#1–Co(3)–O(7)#5 87.97(13) N(3)#4–Co(3)–O(7)#3 87.97(13)
N(3)#1–Co(3)–O(7)#3 92.03(13) O(7)#5–Co(3)–O(7)#3 180.00(6)
N(3)#4–Co(3)–O(9) 90.61(12) N(3)#1–Co(3)–O(9) 89.39(12)
O(7)#5–Co(3)–O(9) 88.66(11) O(7)#3–Co(3)–O(9) 91.33(11)
N(3)#4–Co(3)–O(9)#6 89.39(12) N(3)#1–Co(3)–O(9)#6 90.61(12)
O(7)#5–Co(3)–O(9)#6 91.34(11) O(7)#3–Co(3)–O(9)#6 88.66(11)
O(9)–Co(3)–O(9)#6 179.999(1) O(9)–Co(4)–O(8)#3 98.31(11)
O(9)–Co(4)–O(3)#2 96.82(10) O(8)#3–Co(4)–O(3)#2 82.05(11)
O(9)–Co(4)–N(4)#4 93.90(11) O(8)#3–Co(4)–N(4)#4 85.79(12)
O(3)#2–Co(4)–N(4)#4 164.82(12) O(9)–Co(4)–O(5) 95.37(11)
O(8)#3–Co(4)–O(5) 163.03(11) O(3)#2–Co(4)–O(5) 86.41(11)
N(4)#4–Co(4)–O(5) 103.29(13) O(9)–Co(4)–O(6) 155.69(11)
O(8)#3–Co(4)–O(6) 106.00(11) O(3)#2–Co(4)–O(6) 87.14(11)
N(4)#4–Co(4)–O(6) 87.50(12) O(5)–Co(4)–O(6) 60.83(11)
Symmetry code: #1 – x, 1 – y, 1 – z; #2 x, 3/2 – y, 1/2 + z; #3 1 – x, y – 1/2, 3/2 – z; #4 x + 1, y, z; #5 x, 3/2 – y, z – 1/2; #6 1 – x, 1 – y, 1 – z.
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
![Page 5: A 3D Co framework with alternating vertex- and edge ... · 1 Electronic Supplementary Information A 3D CoII framework with alternating vertex- and edge-sharing Δ-ribbon showing a](https://reader033.vdocuments.pub/reader033/viewer/2022060518/604c689953122853e0128f3a/html5/thumbnails/5.jpg)
5
geometrical parameters pathway magnetic bridges
J1 μ3-OH, μ4-atz, μ2-syn,syn-COO-
J2 μ3-OH, μ4-atz
J3 μ3-OH, μ2-syn,syn-COO-
J4 μ2-COO-, μ2-COO- (single-atom-O bridges)
J5 μ3-OH, μ2-syn,syn-COO-
J6 μ3-OH, μ3-OH
J7 μ3-OH, μ2-syn,syn-COO-, μ4-atz
Fig. S3. Scheme of the Δ-ribbon topology, the superexchange pathways, and the geometrical structural parameters
for the triangles of 1.
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
![Page 6: A 3D Co framework with alternating vertex- and edge ... · 1 Electronic Supplementary Information A 3D CoII framework with alternating vertex- and edge-sharing Δ-ribbon showing a](https://reader033.vdocuments.pub/reader033/viewer/2022060518/604c689953122853e0128f3a/html5/thumbnails/6.jpg)
6
Fig. S4. (a) Perpendicular ribbons of edge- and vertex-sharing Δ-ribbon in 1 linked by two ip2- bridges. (b)
Coordination modes of ip2- ligands.
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
![Page 7: A 3D Co framework with alternating vertex- and edge ... · 1 Electronic Supplementary Information A 3D CoII framework with alternating vertex- and edge-sharing Δ-ribbon showing a](https://reader033.vdocuments.pub/reader033/viewer/2022060518/604c689953122853e0128f3a/html5/thumbnails/7.jpg)
7
Fig. S5. Plot of χMT and χM-1 vs T for 1 under an applied magnetic field of 0.5 KOe (The solid straight lines is
corresponding to the best fit).
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011
![Page 8: A 3D Co framework with alternating vertex- and edge ... · 1 Electronic Supplementary Information A 3D CoII framework with alternating vertex- and edge-sharing Δ-ribbon showing a](https://reader033.vdocuments.pub/reader033/viewer/2022060518/604c689953122853e0128f3a/html5/thumbnails/8.jpg)
8
Fig. S6. Temperature-dependent ac susceptibility recorded under a zero Oe dc field and a 3.5 Oe ac field at
various frequencies.
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011