Research Article
Properties of Metal-Doped Covalent Organic Frameworks and Their Interactions with Sulfur Dioxide
Table 5
NBO analysis at B3LYP/6-31G(d) level of theory for the adsorption complexes SO2/metal@COF-105 (selected values)1.
| | Complex | Donor NBOs | Acceptor NBOs | E(2) (kcal/mol) | E(j)− E(i) (a.u.) | F(i, j) (a.u.) | Principle delocalization types |
| | SO2/Li@COF-105 | BD∗(2) S–O8 | LP∗(2) B1 | 2.87 | 0.01 | 0.009 | Remote | | BD (1) S–O8 | LP∗(1)Li | 1.73 | 0.78 | 0.034 | Remote | | BD (1) S–O7 | LP∗(1)Li | 6.85 | 1.00 | 0.076 | Remote | | CR (2) S | LP∗(1)Li | 7.53 | 9.15 | 0.242 | Remote | | LP (1) S | LP∗(1)Li | 18.79 | 0.76 | 0.109 | Remote | | LP (1) O7 | LP∗(1)Li | 26.25 | 0.91 | 0.141 | Remote |
| | SO2/Na@COF-105 | BD (1) S–O8 | LP∗(1)Na | 1.05 | 1.02 | 0.030 | Remote | | BD (1) S–O7 | LP∗(1)Na | 3.75 | 1.00 | 0.056 | Remote | | CR (2) S | LP∗(1)Na | 3.68 | 9.20 | 0.168 | Remote | | CR (1) O7 | LP∗(1)Na | 2.73 | 19.11 | 0.208 | Remote | | LP (1) S | LP∗(1)Na | 9.35 | 0.75 | 0.076 | Remote | | LP (1) O7 | LP∗(1)Na | 19.47 | 0.90 | 0.120 | Remote |
| | SO2/K@COF-105 | BD (1) S–O7 | LP∗(1)K | 1.60 | 0.99 | 0.036 | Remote | | CR (2) S | LP∗(1)K | 1.66 | 9.33 | 0.113 | Remote | | CR (1) O7 | LP∗(1)K | 1.95 | 19.10 | 0.175 | Remote | | LP (1) S | LP∗(1)K | 4.24 | 0.74 | 0.051 | Remote | | LP (1) O7 | LP∗(1)K | 14.56 | 0.90 | 0.103 | Remote |
| | SO2/Sc@COF-105 | BD∗(1)S–Sc | RY∗(1) O8 | 0.76 | 1.36 | 0.032 | Vicinal | | BD∗(1)S–Sc | BD(1)S–Sc | 6.74 | 0.14 | 0.064 | Geminal | | CR(3)Sc | BD∗(1)S–O7 | 2.70 | 2.77 | 0.080 | Vicinal | | LP(2) O7 | LP∗(1)Sc | 84.93 | 0.73 | 0.225 | Remote | | LP(2) O8 | RY∗(1) Sc | 0.97 | 1.35 | 0.034 | Remote | | LP∗(2)Sc | BD∗(1)S–O7 | 1.70 | 0.18 | 0.038 | Vicinal | | BD(1)S-Sc | LP∗(8)Sc | 0.66 | 0.06 | 0.013 | Geminal |
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1BD denotes the formally occupied 2-center bonding orbital. RY∗ denotes 1-center Rydberg. LP denotes 1-center lone pair. The unstarred and starred labels denote Lewis and non-Lewis NBOs, respectively.
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