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. 2022 Jul 21;7(30):26965–26982. doi: 10.1021/acsomega.2c03834

Table 2. Ground-State Redox Potential vs Ag/AgCl in 0.1 M (Bu4N)PF6–Acetonitrile and Emission Maximum Wavelength, Emission Lifetime, Emission Quantum Yield, and Calculated Excited-State Oxidation Potential.

  acetonitrile at 298 or 296 K
 solid state at 296 K
  E1/2[Re6(23e)/Re6(24e)] vs Ag/AgCl E1/2(L0/L–) vs Ag/AgCl λmax/nm τem/μs Φem Eox[Re6(23e)/Re6(24e)*] vs Ag/AgCl ΣEL of the terminal ligands λmax/nm τem/μs
Complex with the Core-Centered Excited State
[Re6(μ3-S)8Cl6]4– 0.31a   770b 6.3b 0.039b –1.30 –1.44 770b 5.6b
[Re6(μ3-S)8Br6]4– 0.34c   780b 5.4b 0.018b –1.25 –1.32 780b 4.4b
[Re6(μ3-S)8I6]4– 0.36c   800b 4.4b 0.015b –1.19 –1.44 800b 3.4b
[Re6(μ3-S)8Cl5(dmap)]3– ([1-dmap]3–) 0.49   754 0.18, 6.4 0.030 –1.15 –1.05 721 1.7, 4.0
[Re6(μ3-S)8Cl5(PEt3)]3– 0.500d,e   713d 4.13d 0.038d –1.24 –0.86    
[Re6(μ3-S)8Cl5(lut)]3– ([1-lut]3–) 0.52   756 5.8 0.046 –1.12 –0.99 754 1.9, 4.1
[Re6(μ3-S)8Cl5(mpy)]3– ([1-mpy]3–) 0.53   755 4.9 0.022 –1.11 –0.97 747 1.3, 4.2
[Re6(μ3-S)8Cl5(py)]3– ([1-py]3–) 0.54   756 4.6 0.040 –1.11 –0.95 752 0.87, 4.3
trans-[Re6(μ3-S)8Cl4(PEt3)2]2– 0.665d,e   710d 4.74d 0.036d –1.08 –0.28    
cis-[Re6(μ3-S)8Cl4(PEt3)2]2– 0.664d,e   714d 5.60d 0.041d –1.07 –0.28    
trans-[Re6(μ3-S)8Cl4(dmap)2]2– ([2a-dmap]2–) 0.68f   747 1.4, 6.4 0.051 –0.98 –0.66 738 2.2, 5.1
cis-[Re6(μ3-S)8Cl4(dmap)2]2– ([2b-dmap]2–) 0.68f   751 5.9 0.049 –0.97 –0.66 748 0.86, 3.6
trans-[Re6(μ3-S)8Cl4(lut)2]2– ([2a-lut]2–) 0.74   750 4.4 0.039 –0.91 –0.54 743 1.7, 4.8
cis-[Re6(μ3-S)8Cl4(lut)2]2– ([2b-lut]2–) 0.74   747 6.4 0.056 –0.92 –0.54 747 1.7, 5.4
trans-[Re6(μ3-S)8Cl4(mpy)2]2– ([2a-mpy]2–) 0.75f   749f 4.2f 0.031f –0.91 –0.50    
cis-[Re6(μ3-S)8Cl4(mpy)2]2– ([2b-mpy]2–) 0.75f   745f 6.2f 0.057f –0.91 –0.50    
trans-[Re6(μ3-S)8Cl4(bpe)2]2– ([2a-bpe]2–) 0.76g   751g 4.4g 0.024g –0.89 –0.44 738g 0.78, 4.0g
cis-[Re6(μ3-S)8Cl4(bpe)2]2– ([2b-bpe]2–) 0.76g   746g 5.9g 0.036g –0.90 –0.44 718g 0.81, 4.5g
trans-[Re6(μ3-S)8Cl4(py)2]2– ([2a-py]2–) 0.77a   750f 4.5f 0.033f –0.88 –0.46 764 0.48, 3.1
cis-[Re6(μ3-S)8Cl4(py)2]2– ([2b-py]2–) 0.77a   745f 5.1f 0.042f –0.89 –0.46 764 0.60, 2.5
mer-[Re6(μ3-S)8Cl3(PEt3)3]− 0.819d,e   703d 5.68d 0.038d –0.94 0.30    
fac-[Re6(μ3-S)8Cl3(PEt3)3]− 0.831d,e   711d 7.11d 0.041d –0.91 0.30    
[Re6(μ3-S)8(NCS)6]4– 0.84h   745h 10.4h 0.091h –0.82 –0.36    
mer-[Re6(μ3-S)8Cl3(lut)3]− ([3-lut]−) 0.94   742 6.3 0.055 –0.73 –0.09 743 1.8, 5.0
mer-[Re6(μ3-S)8Cl3(py)3]− ([3-py]−) 0.97a   740f 5.9f 0.045f –0.71 0.03    
trans-[Re6(μ3-S)8Cl2(PEt3)4] 0.980d,i   717d,j 7.01d,j 0.042d,j –0.75 0.88    
cis-[Re6(μ3-S)8Cl2(PEt3)4] 1.00d,i   722d,j 6.61d,j 0.049d,j –0.72 0.88    
Complex Involving Marginal Core-Centered and MLCT Excited States
trans-[Re6(μ3-S)8Cl4(ppy)2]2– ([2a-ppy]2–) 0.77g –1.70g 734g 4.1g 0.030g –0.92 –0.50 727g 2.0, 4.1g
cis-[Re6(μ3-S)8Cl4(ppy)2]2– ([2b-ppy]2–) 0.77g –1.65g 720g 4.1g 0.038g –0.95 –0.50 685g 4.9g
mer-[Re6(μ3-S)8Cl3(ppy)3]− ([3-ppy]−) 1.01g,k –1.57g,k 728g 5.7g 0.042g –0.69 –0.03 705g 1.7, 5.3g
mer-[Re6(μ3-S)8Cl3(bpy)3]− ([3-bpy]−) 1.06g,k –1.20g,k 709g 1.01g 0.0057g –0.69 0.09 696g 0.95, 3.1g
Complex Involving the MLCT Excited State
[Re6(μ3-S)8Cl5(ppy)]3– ([1-ppy]3–) 0.53 –1.74 739l 0.33l 0.0089l –1.15 –0.97 690l 0.96, 3.4l
[Re6(μ3-S)8Cl5(bpy)]3– ([1-bpy]3–) 0.55 –1.48 n.d. n.d. n.d.   –0.93 714 0.096, 0.52
[Re6(μ3-S)8Cl5(cpy)]3– ([1-cpy]3–) 0.57 –1.28 n.d. n.d. n.d.   –0.88 753 0.011, 0.051
[Re6(μ3-S)8Cl5(pz)]3– ([1-pz]3–) 0.58 –1.44 n.d. n.d n.d.   –0.87 750 0.088, 0.20
trans-[Re6(μ3-S)8Cl4(bpy)2]2– ([2a-bpy]2–) 0.79f –1.45 (2e)f 763f 0.019f 0.0013f –0.84 –0.42 699g 2.92g
cis-[Re6(μ3-S)8Cl4(bpy)2]2– ([2b-bpy]2–) 0.79f –1.44 (2e)f 768f 0.013f 0.0011f –0.82 –0.42 701g 0.50, 1.91g
trans-[Re6(μ3-S)8Cl4(cpy)2]2– ([2a-cpy]2–) 0.83a –1.19a n.d. n.d. n.d.   –0.32 721 0.19, 1.0
cis-[Re6(μ3-S)8Cl4(cpy)2]2–) ([2b-cpy]2–)) 0.83a –1.18a n.d. n.d. n.d.   –0.32 750 0.050, 0.14
trans-[Re6(μ3-S)8Cl4(pz)2]2–) ([2a-pz]2–)) 0.86f –1.34f 782f 0.029, 0.013f 0.0017f –0.73 –0.30    
cis-[Re6(μ3-S)8Cl4(pz)2]2–) ([2b-pz]2–)) 0.86f –1.33f 785f 0.021f 0.0010f –0.72 –0.30    
Complex Whose Excited State Character Is Not Assigned
trans-[Re6(μ3-S)8Cl2(ppy)4]             0.44 708m  
trans-[Re6(μ3-S)8Br2(ppy)4]             0.48 715m  
trans-[Re6(μ3-S)8Cl2(bpy)4]   –1.07n,o         0.60 725n  
trans-[Re6(μ3-S)8Br2(bpy)4]   –0.93n,o         0.64 730n  
a

Ref (35).

b

Ref (33).

c

Ref (30).

d

Ref (51).

e

In 0.2 M (Bu4N)BF4–acetonitrile.

f

Ref (37).

g

Ref (52).

h

Ref (39).

i

In 0.2 M (Bu4N)BF4–dichloromethane.

j

In dichloromethane.

k

In 0.1 M (Bu4N)PF6–DMSO.

l

Ref (53).

m

Ref (75).

n

Ref (71).

o

In 0.1 M (Bu4N)ClO4–DMSO.