Chemicals of the highest commercial grade available (solvents are from Kanto Chemical, organic compounds are from Tokyo Chemical Industry and metal sources from Wako and Aldrich) were used as received without further purification.

Single crystals suitable for X-ray analysis of cyGdCu were prepared according to the procedure given in the literature [22Okamoto, Y; Nidaira, K; Akitsu, T Environmental dependence of artifact CD peaks of chiral schiff base 3d-4f complexes in soft mater PMMA matrix Int. J. Mol. Sci, 2011, 12, 6966-6979.
[http://dx.doi.org/10.3390/ijms12106966] ].

To a solution of cyGdCu (0.0060 g, 0.0075 mmol) dissolved in methanol (1.5 mL), a solution of potassium tetracyano nickel(II) hydrate (0.0019 g, 0.0075 mmol) dissolved in water (1.5 mL) was added and stirred for 24 h at 298 K. The aqueous solution of potassium tetracyano nickel(II) hydrate played a role in promoting crystallization of good single crystals of cyCu. Purple needle crystals suitable for X-ray crystallography were obtained from the resulting solution (yield 0.0011 g, 32.03 %). Yield 0.0011 g (32.03 %). IR (KBr (cm^-1): 426 (w), 463 (w), 506 (w), 560 (m), 600 (m), 668 (w), 732 (s), 781 (w), 881 (w), 921 (w), 977 (m), 1025 (m), 1108 (w), 1163 (w), 1224 (s), 1242 (s), 1321 (s), 1354 (m), 1390 (w), 1442 (s), 1473 (s), 1542 (m), 1600 (s), 1626 (s) (C=N), 2928 (s), 3504 (s).

Under N₂ atmosphere at 298 K, treatment of tetraethylammonium perchlorate (0.640 g, 2.00 mmol) and potassium tetracyano nickel(II) hydrate (0.259 g, 1.00 mmol) in methanol (50 mL) for 72 h gave rise to tetraethylammonium tetracyanonickel(II) hydrate (a precursor). To a 5 mmol/L methanol solution of potassium tetracyanonickel(II) hydrate (1.5 mL), a precursor cyGdCu (0.0060 g, 0.0075 mmol) in methanol (1.5 mL) was added and stirred for 24 h at 298 K. A few grains of brown prismatic crystals suitable for X-ray crystallography were obtained from the resulting solution. Yield 0.0013 g (15.41 %). IR (KBr (cm^-1): 562 (s), 668 (w), 748 (s), 853 (w), 970 (m), 1027 (w), 1082 (m), 1212 (s), 1242 (s), 1318 (m), 1440 (s), 1473 (s), 1542 (m), 1629 (s) (C=N), 2118 (m) (C≡N), 2839 (w), 2933 (w), 3423 (s).

To a solution of o-vanillin (0.305 g, 2.00 mmol) dissolved in methanol (60 mL), (1R,2R)-(-)-1,2-cyclohexane-diamine (0.114 g, 1.00 mmol) was added and stirred at 313 K for 2 h to give yellow solution of ligand(L1). Nickel(II)acetate tetrahydrate (0.2545 g, 1.00 mmol) was added to the resulting solution to yield muddy brown solution of the complex. After stirring at 313 K for 3 h, lutetium(III)nitrate hexahydrate (0.3642 g 1.00 mmol) was added to the resulting solution and the mixed solution was refluxed for 4 h at 373 K. After cooling the solution, the resulting orange compound was filtered and recrystallized from methanol/diethyl ether to obtain single crystals. Yield 0.5732 g (71.64 %). Anal. Found: C, 33.22 ; H, 2.91 ; N, 8.61 %. Calc. for C₂₂H₂₄LuN₅NiO₁₃: C, 33.02 ; H, 3.02 ; N, 8.75 %. IR (KBr (cm^-1):566 (w), 598 (w), 681 (w),740 (m), 786 (w), 810 (w), 869 (w), 964 (m), 1036 (m), 1077 (m), 1168 (w), 1232 (s), 1321 (s), 1383 (m), 1478 (s), 1520 (s), 1619 (s) (C=N), 1700 (s), 2328 (w), 2944 (w), 3401 (s).

To a solution of o-vanillin (0.305 g, 2.00 mmol) dissolved in methanol (60 mL), (1R,2R)-(-)-1,2-cyclohexane-diamine (0.114 g, 1.00 mmol) was added and stirred at 313 K for 2 h to give yellow solution of ligand (L1). Copper(II)acetate hydrate (0.2027 g, 1.00 mmol) was added to the resulting solution to yield muddy purple solution of the complex. After stirring at 313 K for 3 h, lutetium(III)nitrate hexahydrate (0.3610 g, 1.00 mmol) was added to the resulting solution and the reaction was refluxed for 4 h at 373 K. The solution was evaporated under reduced pressure, and deep brown compound was yielded. This compound was filtered and recrystallized from methanol/diethyl ether to give crystals. Yield 0.5962 g (74.06 %). Anal. Found: C, 33.14; H, 3.06; N, 6.80 %. Calc. for C₂₂H₂₄LuN₅CuO₁₃: C, 32.83; H, 3.01; N, 8.70 %. IR (KBr (cm^-1): 533 (w), 650 (w), 740 (m), 855 (w), 949 (m), 1019 (m), 1070 (m), 1221 (s), 1303 (s), 1383 (m), 1468 (s), 1521 (m), 1630 (s) (C=N), 1652 (s), 2328 (w), 2943 (m), 3399 (s).

To a solution of o-vanillin (0.305 g, 2.00 mmol) dissolved in methanol (60 mL), (1R,2R)-(-)-1,2-cyclohexanediamine (0.114 g, 1.00 mmol) was added and stirred at 313 K for 2 h to give a ligand (L1). Zinc(II)acetate tetrahydrate (0.2243 g, 1.00 mmol) was added to the resulting solution to yield light-yellow solution of the complex. After stirring at 313 K for 3 h, lutetium(III) nitrate hexahydrate (0.3526 g, 1.00 mmol) was added to the resulting solution and the reaction was refluxed for 4 h at 373 K. The solution was evaporated under reduced pressure, and yellow compound was obtained. This compound was filtered and recrystallized from methanol/diethyl ether to obtain single crystals containing (nonstoichometric) CH₄O solvent suitable for X-ray analysis. Yield 0.5732 g (68.57 %). Anal. Found: C, 35.86; H, 3.60; N, 6.62 %. Calc. for C₂₅H₃₁LuN₄ZnO₁₃: C, 35.92; H, 3.74; N, 6.70 %. IR (KBr (cm^-1): 444 (w), 537 (w), 566 (w), 624 (w), 665 (m), 739 (s), 781 (w), 812 (w), 857 (m), 888 (w), 949 (s), 1015 (s), 1073 (m), 1165 (w), 1221 (s), 1268 (s), 1165 (m), 1380 (w), 1384 (m), 1476 (s), 1534 (s), 1556 (m), 1630 (m) (C=N), 1656 (m), 2942 (m), 2424 (s), 3403 (s).

Single crystals suitable for X-ray analysis of diCu were prepared according to the procedure given in the literature [21Akitsu, T; Hirarsuka, T; Shibata, H Chiroptical properties of 3d-4f chiral Schiff base magnetic complexes. Magnets:Types, Uses and Safety; Nova Science Publishers, 2012, pp. 69-84.].

Elemental analyses (C, H, N) were carried out with a Perkin-Elmer 2400II CHNS/O analyzer at Tokyo University of Science. Infrared spectra were recorded using KBr pellets on a JASCO FT-IR 4200 plus spectrophotometer in the range of 4000-400 cm^-1 at 298 K. Diffuse reflectance spectra were measured on a JASCO V-570 UV/VIS/NIR spectrophotometer equipped with an integrating sphere in the range of 800-200 nm at 298 K. Circular dichroism (CD) spectra were measured as KBr pellets on a JASCO J-820 spectropolarimeter in a range of 800-300 nm at 298 K. Fluorescence spectra in the solid state were recorded on a JASCO FP-6200 spectrophotometer at 298 K.

Prismatic single crystals of purple cyCu, brown cyGdCu, brown cyCuKNi, orange cyLuNi, purple cyLuCu, pale yellow cyLuZn, and green diCu were glued on top of a glass fiber and coated with a thin layer of epoxy resin. Intensity data were collected on a Bruker APEX2 CCD diffractometer with graphite monochromated Mo Kα radiation (λ = 0.71073 A). Data analysis was carried out with a SAINT program package. The structures were solved by direct methods with a SHELXS-97 [24Sheldrick, GM A short history of SHELX Acta. Crystallogr. A, 2008, 64, 112-22.
[http://dx.doi.org/10.1107/S0108767307043930] ] and expanded by Fourier techniques and refined by full-matrix least-squares methods based on F² using the program SHELXL-97 [24Sheldrick, GM A short history of SHELX Acta. Crystallogr. A, 2008, 64, 112-22.
[http://dx.doi.org/10.1107/S0108767307043930] ]. A multi-scan absorption correction was applied by a program SADABS. All non-hydrogen atoms were readily located and refined by anisotropic thermal parameters. All hydrogen atoms were located at geometrically calculated positions and refined using riding models.

The crystallographic data for “cyCu, cyGdCu, and CyCuKNi”, “cyLuM (M=Ni, Cu, and Zn)”, and “diCu”are summarized in Tables 1, 2, and 3, respectively.

Table 1

Crystal data and structure refinement for cyCu, CyGdCu, and cyCuKNi.

Table 2

Crystal data and structure refinement for cyLuM(M=Ni, Cu, Zn).

Table 3

Crystal data and structure refinement for diCu.

Complex cyCu crystallizes in monoclinic, space group P2₁ with Z = 2. As shown in Figs. (2) and S1, the asymmetric unit of cyCu contains crystallographically two independent molecules of four-coordinated and five coordinated mononuclear Cu(II) complexes. One of the Cu(II) complex affords a four-coordinated square planar [CuN₂O₂] geometry with the four donor atoms of the tetradentete Schiff base forming the equatorial plane with Cu1–N1, Cu1-N2, Cu1-O2, and Cu1-O4 distances ranging from 1.8946(19) to 1.937(2) Å (Table 4).

Fig. (2) Molecular structures of cyCu showing selected atom labeling scheme. Hydrogen atoms are omitted for clarity.

Table 4

Selected bond lengths (Å) and angles(°) for cyCu.

The other Cu(II) complex affords a five-coordinated square pyramidal [CuN₂O₃] geometry with additional aqua ligand occupying the axial sites with Cu2–N3, Cu2-N4, Cu2-O6, and Cu2-O8 distances ranging from 1.9114(19) to 1.951(2) Å and axial O atom from coordinate aqua ligand with Cu2–O9 distance of 2.453(2) Å (Table 4). The displacement of Cu1 and Cu2 from the A-plane and A’-plane (Fig. 3) is 0.0198(13) Å and 0.1407(13) Å, respectively. The chiral (1R,2R)-(-)-1,2-cyclohexanediamine moieties adopt a λ configuration with torsion angles N1-C9-C20-N2 = -47.2(3)° and N3-C31-C42-N4 = -45.8(3)°, respectively.

Fig. (3) Definition of mean planes for comparison of common moieties.

The dihedral angles between the B-plane and C-plane and between the B’-plane and C’-plane are 13.86(6) and 5.45(5)°, respectively. The angles between the A-plane and B-plane and between the A’-plane and B’-plane are 9.65(4) and 8.77(4)°, respectively. And the angles between the A-plane and C-plane and between the A’-plane and C’-plane are 4.21(6) and 3.42(3)°, respectively. Moreover, the angles between the A-plane and D-plane, between the A-plane and E-plane, and between the D-plane and E-plane are 8.24(4), 6.82(6), and 14.65(6)°, and between the A’-plane and D’-plane, between the A’-plane and E’-planes, and between the D’-plane and E’-plane are 7.84, 4.81, and 6.53°, respectively.

The displacement of O9 from the F-plane is 0.6961(32) Å for the four-coordinated molecule taking planar structure (see Fig. 4). Whereas the displacement of O10 from the F’-plane is 0.9007(33) Å for the five-coordinated molecule (see Fig. 4). Since axial water ligands and crystalline water are in the same side, the overall molecule takes slightly distorted umbrella structure towards the opposite side of the axial ligand (see Fig. 5).

Fig. (4) Distortion of L (I and II distort toward the same side and the opposite side of the axial ligand).

Fig. (5) Distortion of overall molecular structures.

Complex cyGdCu crystallizes in monoclinic, space group P2₁ with Z = 4. As shown in Fig. (6) and S2, the Gd(III) ion affords a ten-coordinated environment with distorted square pyramidal towards bridging nitrate ligands. While Cu(II) ion affords a four-coordinated square planar [CuN₂O₂] geometry with Cu1–N1, Cu1-N2, Cu1-O2, and Cu1-O4 distances ranging from 1.898(5) to 1.916(5) Å (Table 5), the displacement of Cu1 from the A-plane is 0.0357(25) Å (see Fig. 3). The chiral (1R,2R)-(-)-1,2-cyclohexanediamine moiety adopts a λ configuration, with torsion angle N1-C9-C20-N2 = -49.1(6)°.

Fig. (6) Molecular structures of cyGdCu showing selected atom labeling scheme. Hydrogen atoms are omitted for clarity.

Table 5

Selected bond lengths (Å) and angles(°) for cyGdCu.

The overall molecular structure of planar is an umbrella shape. The dihedral angle between the B-plane and C-plane is 24.82°. The angles between the A-plane and B-plane and between the A-plane and C-plane are 19.18 and 6.45°, respectively. Moreover, the angles between the A-plane and D-plane, between the A-plane and E-planes, and between the D-plane and E-plane are 13.70, 5.94 and, 19.39°, respectively. The displacement of Lu1 from the F-plane is 0.4675(29) Å.

Complex cyCuKNi crystallizes in triclinic, space group P1 with Z = 1. As shown in Figs. (7 and S3), there are four-coordinated and five-coordinated K(I) ions in the same molecule. Moreover, square planar [Ni(CN)₄]^2- units are bridged to form a one-dimensional chain as shown in Fig. (8). The Cu(II) ion affords a five-coordinated square pyramidal [CuN₃O₂] geometry with Cu1–N1, Cu1-N2, Cu1-O2, and Cu1-O4 distances ranging from 1.885(7) to 1.989(8) Å and the axial Cu1-N5 (cyanide) bond distance being 2.435(8) Å (Table 6). The displacement of Cu1 from the A-plane (see Fig. 3) is 0.1640(32) Å. The chiral (1R,2R)-(-)-1,2-cyclohexanediamine moiety adopts a λ configuration, with torsion angle N1-C9-C20-N2 =43.1(8)°.

Fig. (7) Molecular structures of cyCuKNi showing selected atom labeling scheme. Hydrogen atoms are omitted for clarity.

Fig. (8) Crystal packing of cyCuKNi viewed down from the a axis.

Table 6

Selected bond lengths (Å) and angles(°) for cyCuKNi.

The dihedral angle between the B-plane and C-plane is 6.06°. The angles between the A-plane and B-plane and between the A-plane and C-plane are 9.68, and 3.63°, respectively. Moreover, the angles between the A-plane and D-plane, between the A-plane and E-planes, and between the D-plane and E-plane are 9.49, 4.89, and 6.51°, respectively.

The displacement of K1 from the F-plane is 0.0307(50) Å, and there is K ion almost in the F-plane. Detailed structural description for the other molecules with Cu2 is omitted because of similarity.

Complexes cyLuNi, cyLuCu, and cyLuZn crystallize in triclinic, space group P1 with Z = 2, P2₁ with Z = 4, and P1 with Z = 2, respectively. As shown in Figs. (9-11 and S4- S6), Lu(III) ion affords a ten-, nine-, and nine-coordinated environment with distorted square pyramidal from the plane made by two nitrate ligands. Ni(II) ion affords a four-coordinated square planar [NiN₂O₂] geometry with Ni1–N1, Ni1-N2, Ni1-O2, and Ni1-O4 distances ranging from 1.814(14) to 1.888(14) Å (Table 7). Cu(II) ion affords a five-coordinated square pyramidal [CuN₂O₃] geometry with Cu1-N1, Cu1-N2, Cu1-O2, and Cu1-O4 distances ranging from 1.893(5) to 1.920(4) Å and axial O atom from bridging nitrate ligand with Cu1–O9 distance of 2.399(5) Å (Table 8). Zn(II) ion affords a five-coordinated square pyramidal [ZnN₂O₃] geometry with Zn1–N1, Zn1-N2, Zn1-O2, and Zn1-O4 distances ranging from 2.015(9) to 2.054(9) Å and axial O atom from bridging acetate ligand with Zn1–O9 distance of 1.996(9) Å (Table 9). The displacement of Ni1, Cu1, and Zn1 atoms from the A-plane (see Fig. 3) is 0.0071(85) Å, 0.0619(20) Å, and 0.6150(45) Å, respectively. The chiral (1R,2R)-(-)-1,2-cyclohexanediamine group adopts a λ configuration, with torsion angle N1-C9-C20-N2 = -43.3(13)°, -42.0(5)°, and -43.4(9)°, respectively.

Fig. (9) Molecular structures of cyLuNi showing selected atom labeling scheme. Hydrogen atoms are omitted for clarity.

Fig. (10) Molecular structures of cyLuCu showing selected atom labeling scheme. Hydrogen atoms are omitted for clarity.

Fig. (11) Molecular structures of cyLuZn showing selected atom labeling scheme. Hydrogen atoms are omitted for clarity.

Table 7

Selected bond lengths (Å) and angles(°) for cyLuNi.

Table 8

Selected bond lengths (Å) and angles(°) for cyLuCu.

Table 9

Selected bond lengths (Å) and angles(°) for cyLuZn.

The dihedral angles between the B-plane and C-plane are 3.08°, 16.91°, and 32.59°, respectively. The angles between the A-plane and B-plane and between the A-plane and C-plane are 8.98, and 6.00°, 10.08, and 10.99°, and 11.36 and 21.32°, respectively. Moreover, the angles between the A-plane and D-plane, between the A-plane and E-planes, and between the D-plane and E-plane are 11.34, 7.41, and 5.59°, 1.44, 9.78, and 11.02°, and 14.07, 23.01, and 37.07°, respectively.

Complex diCu crystallizes in monoclinic, space group P2₁ with Z = 4. As shown in Figs. (12 and S7), Cu(II) ion affords a five-coordinated square pyramidal [CuN₂O₃] geometry with Cu1–N1, Cu1-N2, Cu1-O2, Cu1-O4 distances ranging from 1.921(2) to 1.964(3) Å and axial O atom from coordinate aqua ligand with Cu1–O9 distance of 2.340(3) Å (Table 10). The displacement of Cu1 atom from the A-plane (see Fig. 3) is 0.1634(13) Å. The chiral (1R,2R)-(+)-1,2-diphenylethylenediamine group adopts a λ configuration, with torsion angle N1-C9-C24-N2 and C10-C9-C24-C25 = -47.6(3)° and 58.0(3)°, respectively.

Fig. (12) Molecular structures of diCu showing selected atom labeling scheme. Hydrogen atoms are omitted for clarity.

Table 10

Selected bond lengths (Å) and angles(°) for diCu.

The dihedral angle between the B-plane and C-plane is 9.00°. The angles between the A-plane and B-plane and between the A-plane and C-plane are 11.36 and 8.44°, respectively. Moreover, the angles between the A-plane and D-plane, between the A-plane and E-planes, and between the D-plane and E-plane are 14.12, 4.90, and 15.02°, respectively.

Two axial water ligands of two molecules face each other inside the two dimeric molecules (see Fig. 4) and the displacement of O10 from the F-plane is 0.7791(35) Å. The overall molecular structure is slightly distorted umbrella shape to the opposite direction of the axial ligand (see Fig. 5).

As shown in Figs. (3-5), the least square mean planes (A-plane , B-plane, C-plane, D-plane, E-plane, and F-plane) are defined using the atom groups (c/k/w/o, d/e/f/g/h/i , p/q/r/s/t/u , c/d/i/j/k ,o/p/u/v/w, and b/c/o/n) for the molecule with M1 atom. Similarly, the least square mean planes (A’-plane , B’-plane, C’-plane, D’-plane, E’-plane, and F’-plane) are defined for the molecule with M atom.

Similar to previous binuclear 3d-4f complexes [10Koner, R; Lee, GH; Wang, Y; Wei, HH; Mohanta, S Two new diphenoxo-bridged discrete dinuclear Cu(II)Gd(III) compounds with cyclic diimino moieties: syntheses, structures, and magnetic properties Eur. J. Inorg. Chem, 2005, 8, 1500-1505.
[http://dx.doi.org/10.1002/ejic.200400858] -13Jana, A; Majumder, S; Carrella, L; Nayak, M; Weyhermueller, T; Dutta, S; Schollmeyer, D; Rentschler, E; Koner, R; Mohanta, S Syntheses, structures, and magnetic properties of diphenoxo-bridged Cu(II)Ln(III) and NiII(low-spin)Ln(III) compounds derived from a compartmental ligand (Ln = Ce-Yb) Inorg. Chem, 2010, 49, 9012-9025.
[http://dx.doi.org/10.1021/ic101445n] , 20Hayashi, T; Shibata, H; Orita, S; Akitsu, T Variety of structures of binuclear chiral schiff base Ce(III)/Pr(III)/Lu(III)-Ni(II)/Cu(II)/ Zn(II) complexes Eur. Chem. Bull, 2013, 2, 49-57.-22Okamoto, Y; Nidaira, K; Akitsu, T Environmental dependence of artifact CD peaks of chiral schiff base 3d-4f complexes in soft mater PMMA matrix Int. J. Mol. Sci, 2011, 12, 6966-6979.
[http://dx.doi.org/10.3390/ijms12106966] ], Lu(III) ions of most of the complexes described in this paper adopt ten-coordinated environment. However, nine-coordinated Lu(III) ions are also found for diLuZn [20Hayashi, T; Shibata, H; Orita, S; Akitsu, T Variety of structures of binuclear chiral schiff base Ce(III)/Pr(III)/Lu(III)-Ni(II)/Cu(II)/ Zn(II) complexes Eur. Chem. Bull, 2013, 2, 49-57.], cyLuCu, and cyLuZn, and both nine- and ten-coordinated Lu(III) ions are found for diLuCu [20Hayashi, T; Shibata, H; Orita, S; Akitsu, T Variety of structures of binuclear chiral schiff base Ce(III)/Pr(III)/Lu(III)-Ni(II)/Cu(II)/ Zn(II) complexes Eur. Chem. Bull, 2013, 2, 49-57.]. Formation of nine-coordinated Lu(III) environment is attributed to the smallest ionic radii due to lanthanide contraction as well as significantly steric hindrance of nitrate ions to eliminate [10Koner, R; Lee, GH; Wang, Y; Wei, HH; Mohanta, S Two new diphenoxo-bridged discrete dinuclear Cu(II)Gd(III) compounds with cyclic diimino moieties: syntheses, structures, and magnetic properties Eur. J. Inorg. Chem, 2005, 8, 1500-1505.
[http://dx.doi.org/10.1002/ejic.200400858] -13Jana, A; Majumder, S; Carrella, L; Nayak, M; Weyhermueller, T; Dutta, S; Schollmeyer, D; Rentschler, E; Koner, R; Mohanta, S Syntheses, structures, and magnetic properties of diphenoxo-bridged Cu(II)Ln(III) and NiII(low-spin)Ln(III) compounds derived from a compartmental ligand (Ln = Ce-Yb) Inorg. Chem, 2010, 49, 9012-9025.
[http://dx.doi.org/10.1021/ic101445n] , 20Hayashi, T; Shibata, H; Orita, S; Akitsu, T Variety of structures of binuclear chiral schiff base Ce(III)/Pr(III)/Lu(III)-Ni(II)/Cu(II)/ Zn(II) complexes Eur. Chem. Bull, 2013, 2, 49-57.-22Okamoto, Y; Nidaira, K; Akitsu, T Environmental dependence of artifact CD peaks of chiral schiff base 3d-4f complexes in soft mater PMMA matrix Int. J. Mol. Sci, 2011, 12, 6966-6979.
[http://dx.doi.org/10.3390/ijms12106966] ].

Bridged structures for cyLuCu, cyLuZn, and diLuZn [20Hayashi, T; Shibata, H; Orita, S; Akitsu, T Variety of structures of binuclear chiral schiff base Ce(III)/Pr(III)/Lu(III)-Ni(II)/Cu(II)/ Zn(II) complexes Eur. Chem. Bull, 2013, 2, 49-57.] may be ascribed to axial ligands of Cu(II) and Zn(II) complexes. Distortion of Lu(III) coordination environment toward the axial ligand side may be due to stabilization of bond lengths (Fig. 4). Overall molecular shape also depends on flexibility of 3d ions, namely flexible Cu(II) and Ni(II) for flexible while rigid Zn(II) for bent ones (Fig. 5).

Figs. (13 and S8) show CD spectra for cyCu and cyCuKNi and diffuse reflectance electronic spectra for cyCu and cyCuKNi, respectively. Figs. ( S9 and S10) show CD spectra for cyLuNi, cyLuCu, and cyLuZn and diffuse reflectance electronic spectra for cyLuNi, cyLuCu, and cyLuZn, respectively.

Fig. (13) Solid-state CD spectra for cyCu,and cyCuKNi.

The d-d bands (only for Ni(II) or Cu(II) moieties) and CT bands of CD spectra appeared at about 16000-18000 cm^-1 and 24500-26800 cm^-1, respectively. The corresponding d-d bands of electronic spectra appeared at about 18400-18600 cm^-1, the changes of which are attributed to substitution and/or coordination environment of 3d metal ions [20Hayashi, T; Shibata, H; Orita, S; Akitsu, T Variety of structures of binuclear chiral schiff base Ce(III)/Pr(III)/Lu(III)-Ni(II)/Cu(II)/ Zn(II) complexes Eur. Chem. Bull, 2013, 2, 49-57., 21Akitsu, T; Hirarsuka, T; Shibata, H Chiroptical properties of 3d-4f chiral Schiff base magnetic complexes. Magnets:Types, Uses and Safety; Nova Science Publishers, 2012, pp. 69-84.].

Fig. (14) depicts fluorescence spectra of cyLuZn at 300 K in the solid states. Under this condition determined based on the electronic spectra, florescence peak for cyLuZn appeared at 460 nm due to the ligand. Unfortunately, the other complexes could not be observed in the fluorescence spectra in the solid state under the same conditions.

Fig. (14) Solid-state fluorescence spectra (λex = 360 nm) for cyLuZn at 300 K.