Theoretical and Experimental Spectroscopic Study on 2-Chloro-3-(substituted-phenylamino)-1,4-naphthoquinone Derivatives

Dias, Flaviana R. F; Campos, Vinícius R; Moraes, Raphael S. M. de; Souza, Nelson A; Cunha, Anna C; Lage, Mateus R; Ferreira, Glaucio B

doi:10.21577/0103-5053.20220104

Flaviana R. F Dias

conceptualization

data curation

formal analysis

investigation

methodology

supervision

validation

writing original draft

review and editing

Departamento de Química Orgânica, Instituto de Química, Universidade Federal Fluminense, Campus do Valonguinho, 24020-141 Niterói-RJ, Brazil

Vinícius R Campos

conceptualization

data curation

formal analysis

investigation

methodology

writing original draft

review and editing

Departamento de Química Orgânica, Instituto de Química, Universidade Federal Fluminense, Campus do Valonguinho, 24020-141 Niterói-RJ, Brazil

Raphael S. M. de Moraes

data curation

formal analysis

investigation

methodology

validation

visualization

writing original draft

review and editing

Departamento de Química Orgânica, Instituto de Química, Universidade Federal Fluminense, Campus do Valonguinho, 24020-141 Niterói-RJ, Brazil

https://orcid.org/0000-0002-0508-6937

Nelson A Souza

conceptualization

formal analysis

investigation

methodology

validation

review and editing

Departamento de Química Orgânica, Instituto de Química, Universidade Federal Fluminense, Campus do Valonguinho, 24020-141 Niterói-RJ, Brazil

Anna C Cunha

conceptualization

data curation

formal analysis

investigation

project administration

supervision

writing original draft

review and editing

Departamento de Química Orgânica, Instituto de Química, Universidade Federal Fluminense, Campus do Valonguinho, 24020-141 Niterói-RJ, Brazil

Mateus R Lage

Data curation

formal analysis

investigation

methodology

validation

writing original draft

review and editing

Universidade Federal do Maranhão, Campus Balsas, Rua José Leão, 484, Centro, 65800-000 Balsas-MA, Brazil

Glaucio B Ferreira ^**e-mail: glauciobf@gmail.com

conceptualization

data curation

formal analysis

funding acquisition

investigation

methodology

project administration

supervision

validation

writing original draft

Departamento de Química Inorgânica, Instituto de Química, Universidade Federal Fluminense, 21945-970 Rio de Janeiro-RJ, Brazil

https://orcid.org/0000-0002-3205-3743

*e-mail: glauciobf@gmail.com

Editor handled this article: Brenno A. D. Neto (Associate)

Geometric parameter / Å	1a	X-ray^a a Reference 54;	1b	X-ray^b b reference 55;
C=C_{(Benz. and Naphtq.)}	1.361-1.517	1.367-1.508	1.362-1.517	1.374-1.500
C=O_(Naphtq.)	1.212-1.216	1.210-1.227	1.212-1.216	1.218-1.229
N-C_{(Benz. and Naphtq.)}	1.349-1.417	1.335-1.410	1.347-1.419	1.345-1.412
C-C_(-CH3)			1.505	1.507
C-Cl_(Naphtq.)	1.738	1.732	1.739	1.727
C-C-C_{(Benz. and CH3)} C-N-C_{(Benz. and Naphtq.)}	130.14	128.82	121.02 130.07	121.30 128.95
C-N-C-C_{(Benz. and Naphtq.)}	29.63	21.34	28.31	25.16
	1c	X-ray^c c this work;	1d	X-ray^d d reference 56. Benz.: benzene ring; Naphtq.: naphthoquinone ring.
C=C_{(Benz. and Naphtq.)}	1.363-1.518	1.370-1.441	1.361-1.517	1.364-1.502
C=O_(Naphtq.)	1.212-1.217	1.207-1.230	1.212-1.216	1.218-1.223
N-C_{(Benz. and Naphtq.)}	1.345-1.421	1.345-1.415	1.348-1.419	1.347-1.419
C-O_(-OCH3)	1.355-1.420	1.372-1.422	1.353-1.429	1.356-1.412
C-Cl_(Naphtq.)	1.741	1.735	1.739	1.717
C-O-C_{(Benz. and CH3)} C-N-C_{(Benz. and Naphtq.)}	118.42 130.11	117.15 127.69	115.10-118.37 130.10	117.32-118.92 128.43
C-N-C-C_{(Benz. and Naphtq.)} C-O-C-C_{(Benz. and CH3)}	25.18 0.24	29.39 1.84	28.64 0.87-73.34	34.79 3.06-6.52

Experimental wavenumber / cm^-1		Calculated wavenumber / cm^-1	IR intensity / cm^-1	Raman intensity / cm^-1	PED / %
Infrared	Raman	Calculated wavenumber / cm^-1	IR intensity / cm^-1	Raman intensity / cm^-1	PED / %
3234		3539	234.03	1312	xυ_{NH Naphtq.} (100)
	3066	3222	7.32	1534	υ_{CH Benz. Sym.} (90)
3062		3216	20.97	245	υ_{CH Benz. Asym.} (90)
3039	3040	3208	20.85	437	υ_{CH Benz. Asym.} (86)
1674	1675	1781	338.78	7980	υ_{C=O Naphtq.} (85)
1635	1635	1754	318.10	11942	υ_{C=O Naphtq.} (81)
1603	1604	1683	101.46	13764	υ_{CC Naphtq.} + υ_{CC Benz.} (63)
1591		1670	224.70	515	υ_{CC Naphtq.} + υ_{CC Benz.} (48)
	1577	1666	105.70	204	υ_{CC Benz.} (57)
1558	1561	1644	928.64	11886	υ_{CC Naphtq.} (51)
1506	1515	1576	837.28	2959	υ_{CC Naphtq.} (21); δ_{HNC Naphtq.} (54)
1489	1488	1545	39.82	631	r_{HCCH Benz.} (50)
	1480	1536	55.73	173	r_{HCCH Naphtq.} (49); δ_{CCC Naphtq.} (23)
1460	1459	1508	6.47	97	υ_{CC Naphtq.} (26); r_{HCCH Naphtq.} (51)
1442	1446	1499	72.85	292	υ_{CC Benz.} (23); r_{HCCH Benz.} (40)
1329	1329	1371	188.34	1994	υ_{CC Naphtq.} (57)
	1316	1364	31.14	264	r_{HCCH Benz.} (77)
	1305	1348	5.51	5563	υ_{CC Naphtq. Asym} + υ_{CC Benz.Asym.} (46)
1286		1318	624.32	1993	υ_{CC Naphtq. Asym.} (13); υ_{CC Benz. Asym.} (40)
	1255	1290	295.91	4458	υ_{CC Naphtq.} + υ_{NC Naphtq.} + υ_{CN Benz.} (26)
1240		1270	215.12	2296	υ_{CC Naphtq. Asym.} (15); δ_{HCC Naphtq.} (24)
1190	1193	1226	25.46	704	υ_{CC Naphtq. Asym.} + υ_{NC Naphtq. Sym.} + υ_{CN Benz. Sym.} (41)
1173	1174	1202	3.23	937	υ_{CC Naphtq. Asym.} + υ_{CC Benz. Asym.} (12); δ_{HCC Benz.} (71)
1161	1164	1186	39.14	1385	δ_{HCC Naphtq.} (74)
	1153	1180	3.25	236	δ_{HCC Benz.} (71)
1140	1140	1169	144.27	3593	υ_{CC Naphtq. Asym.} (27); δ_{HCC Naphtq.} (13)
1089	1091	1124	1.18	194	r_{HCCH Naphtq.} (30); δ_{CCC Naphtq.} (17)
1076		1115	34.39	346	υ_{CCBenz. Asym.} (35); r_{HCCH Benz.} (37)
1047	1048	1062	24.12	262	υ_{CC Benz.} (43); δ_{CCC Benz.} (13); r_{HCCH Benz.} (21)
1016	1017	1049	72.87	4998	υ_{CC Naphtq.} (39)
997	1002	1028	5.41	4739	υ_{CC Benz.} (24); δ_{CCC Benz.} (66)
982	977	1011	0.13	91	τ_{HCCH Benz.} (68); τ_{CCCC Benz.} (20)
921	925	956	26.66	503	ω_{HCC Benz.} (54)
899	898	930	8.32	729	δ_{CNC Benz.} + δ_{CCN Naphtq.} (14); τ_{HCCH Benz.} (23)
	850	868	38.03	1306	ω_{HCCH Benz.} (46)
848		866	54.80	327	υ_{CCl Naphtq.} (13); ω_{HCCH Benz.} (44)
	810	823	0.35	248	τ_{HCCH Naphtq.} (10); ω_{CC=O Naphtq.} + τ_{CCCC Naphtq.} (59)
800	801	821	34.13	258	ω_{CCC Benz.} (10)
789	792	789	69.38	268	ω_{HCCH Benz.} (58)
756		752	70.09	252	ω_{HCCH Naphtq.} (33); ω_{CC=O Naphtq.} (35)
717	722	720	62.40	71	ω_{HCCH Benz.} (40); τ_{CCCC Benz.} (50)
692	690	712	27.48	146	τ_{CCC Naphtq.} (11); τ_{CCN Naphtq.} + τ_{CC=O Naphtq.} (37)
665	665	683	8.98	1174	δ_{CCC Naphtq.} (32)
640	643	650	10.37	2122	δ_{CCC Naphtq.} (11); δ_{CC=O Naphtq.} + ω_{CCN Benz.} (12); ω_{CCC Benz.} (10)
624	627	636	8.68	3895	δ_{CCC Benz.} (58)
610	616	613	71.57	4150	δ_{CCC Naphtq.}+δ_{CCC Benz.} (12); τ_{HNC Naphtq.} (32)

Experimental wavenumber / cm^-1		Calculated wavenumber / cm^-1	IR intensity / cm^-1	Raman intensity / cm^-1	PED / %
Infrared	Raman	Calculated wavenumber / cm^-1	IR intensity / cm^-1	Raman intensity / cm^-1	PED / %
3221	3228	3539	238.56	1401	υ_{NH Naphtq.} (100)
3062	3062	3206	13.16	811	υ_{CH Benz. Asym.} (91)
3030		3189	24.00	293	υ_{CH Benz. Asym.} (89)
2958		3136	23.91	458	υ_{CH Subst. Asym.} (100)
2921	2921	3111	25.67	541	υ_{CH Subst. Asym.} (99)
2852		3052	37.99	1553	υ_{CH Subst. Sym.} (99)
1674	1675	1781	329.78	8251	υ_{C=O Naphtq.} (85)
1633	1636	1752	285.53	13427	υ_{C=O Naphtq.} (81)
	1613	1693	21.50	15414	υ_{CC Benz. Asym.} (63); δ_{HCC Benz.} (16)
1593	1596	1672	245.42	2083	υ_{CC Naphtq. Sym.} (48)
1558	1563	1644	978.55	13802	υ_{CC Naphtq. Asym.} (53)
1515	1523	1578	836.90	4310	υ_CN (24); δ_{HNC Naphtq.} (33); δ_{HCC Benz.} (12)
1494		1562	133.29	313	δ_{HNC Naphtq.} (27); δ_{HCC Benz.} (32)
1459	1459	1536	59.98	169	δ_{CCC Naphtq.} (12); δ_{HCC Naphtq.} (53)
1410	1409	1494	44.90	367	δ_{H3CC Subs.} (23); τ_{HCH Subst}_. (48)
1375	1378	1456	12.77	205	υ_{CC Benz. Asym.} (28); δ_{HCC Benz.} (26); τ_{HCC Subst.} (20)
1329	1326	1371	224.18	2698	υ_{CC Naphtq. Asym.} (40)
1311	1314	1344	8.23	5104	υ_{CCNaphtq. Asym.} (10); ρ_{HCCH Benz.} (23)
1298	1303	1334	130.14	946	υ_{CC Naphtq.} (26); ρ_{HCCH Benz.} + ρ_{HCCH Naphtq.} (12)
1284	1289	1315	632.59	2286	υ_{CC Naphtq. Asym.} + υ_{CC Benz. Asym.} (47)
1240		1291	227.72	5013	υ_{CCNaphtq. Asym.} + υ_{CC Benz. Asym.} (16); υ_{NC Benz.} (13)
	1212	1270	201.24	2201	υ_{CC Naphtq. Asym.} (12); δ_{HCC Naphtq.} (26)
1190	1191	1250	14.62	1046	υ_{CC Benz.Asym.} + υ_{CH3-C Subst}_. (53); δ_{HCC Benz.} (20)
1174	1176	1229	22.77	740	υ_{CC Benz. Sym.} (10); υ_{NC Naphtq.} (16); υ_{NC Benz.} (12)
1157	1160	1206	6.27	1726	δ_{HCCH Benz.} (72)
1140	1141	1170	140.70	3564	υ_{CC Naphtq.} (30)
1109		1144	29.81	108	υ_{CC Benz. Asym.} (22); δ_{HCCH Benz.} (63)
1047		1079	11.40	69	υ_{CC Naphtq.} (25); ρ_{HCC Naphtq.} (21)
1018		1050	103.10	6412	υ_{CC Naphtq. Asym.} (50)
984		1027	1.32	4	τ_{HCCH Naphtq.} (78); ω_{CCCC Naphtq.} (11)
964	962	1016	1.35	138	τ_{HCH Subs.} (60); ω_{HCC Subst.} (11)
943	944	986	8.23	232	τ_{HCCH Benz.} (74)
914	915	940	27.23	1522	δ_{CCCl Naphtq.} + δ_{CCN Naphtq.} + δ_{CNC Naphtq.} (30)
848	852	872	65.57	1664	υ_{CC Benz. Sym.} + υ_{CCl Naphtq.} (21); δ_{CCC Naphtq.} (16)
818	817	842	70.86	1245	υ_{CCl Naphtq.} + υ_{CC Benz. Sym} + υ_{CC Naphtq. Sym} (40)
804		829	15.42	131	ω_{HCCH Naphtq.} (45); ω_{CC=O Naphtq.} (28)
787		776	18.83	264	ω_{CCC Benz.} + ω_{CCC Naphtq.} (14)
758	757	752	69.96	457	ω_{HCCH Naphtq.} (29); ω_{CC=O Naphtq.} (30)
	744	744	24.12	350	ω_{CNC Benz.} + ω_{CCC Benz.} (20)
716	720	711	26.62	140	τ_{HCCH Naphtq.} (11); ω_{CCC Naphtq.} (18); τ_{CCC Naphtq.} (19)
679	674	682	11.17	1077	τ_{CCC Naphtq.} + δ_{CCN Naphtq.} + τ_{CNC Naphtq.} + ω_{CCC Benz.} + τ_{CCN Benz.} (23)
660	659	660	11.53	850	δ_{CCC Naphtq.} + δ_{CCN Benz.} (61)
640	641	643	27.06	8255	δ_{CCC Naphtq.} (21); ω_{HNC Naphtq.} (21)
613	614	610	109.14	16578	ω_{HNC Naphtq.} (63)

Experimental wavenumber / cm^-1		Calculated wavenumber / cm^-1	IR intensity / cm^-1	Raman intensity / cm^-1	PED / %
Infrared	Raman	Calculated wavenumber / cm^-1	IR intensity / cm^-1	Raman intensity / cm^-1	PED / %
3247		3538	244.68	1409	υ_{NH Naphtq.} (100)
	3069	3233	11.05	1245	υ_{CH Naphtq. Sym.} (100)
	3048	3219	6.26	965	υ_{CH Benz. Asym.} (94)
3040		3217	7.93	791	υ_{CH Naphtq. Asym.} (90)
	3017	3205	3.42	448	υ_{CH Naphtq. Asym.} (92)
2960		3169	26.41	565	υ_{CH Subst. Asym.} (100)
2920		3107	44.54	316	υ_{CH Subst. Asym.} (100)
2852		3041	59.37	729	υ_{CH Subst. Sym.} (100)
1674	1675	1781	331.62	8358	υ_{C=O Naphtq.} (86)
1633	1636	1750	264.12	14394	υ_{C=O Naphtq.} (81)
	1610	1691	79.28	16254	υ_{CC Benz.} (58); δ_{CCH Benz.} (12)
1593	1592	1672	230.06	2445	υ_{CC Naphtq.} (61)
1564	1565	1643	968.97	14544	υ_{CC Naphtq.} + υ_{CN Naphtq.} (56)
1514	1517	1578	1053.81	4028	δ_{HNC Benz.} (40); δ_{HCC Benz.} (10)
1493	1500	1560	181.45	406	δ_{HNC Benz}_. (20); δ_{HCC Benz.} (37)
1454	1455	1536	57.24	148	δ_{HCC Naphtq.} (53); δ_{CCC Naphtq.} (14)
1439	1442	1505	58.98	356	δ_{HCH Subst.} (69); τ_{H3CO Subst.} (23)
1417	1419	1492	14.14	449	δ_{HCH Subst.} (71); τ_{H3CO Subst.} (22)
1328		1373	305.91	5685	υ_{CC Naphtq. Asym.} (52)
1311		1358	42.23	5984	υ_{CN Naphtq. Asym.} + υ_{CC Benz}_. _Asym. + υ_{CC Naphtq. Asym.} + υ_{C-O Benz. Asym.} (49)
	1303	1340	31.50	2826	ρ_{HCCH Naphtq.}+ρ_{HCCH Benz.} (41); υ_{CC Naphtq. Asym.} (12)
1284		1291	915.32	1107	υ_{CO Benz.} + υ_{CC Benz. Asym.} (50); ρ_{HCCH Benz.} (11)
	1268	1290	62.71	3507	υ_{CN Benz}_. + υ_{CC Benz. Asym.} (33); ρ_{HCCH Naphtq.}
1234	1241	1271	183.13	2275	υ_{CC Naphtq. Sym}_.(17); δ_{HCC Naphtq.} (32)
1194	1193	1197	35.89	1920	υ_{CC Benz. Sym.} (12); δ_{HCC Benz.} (70)
1180	1172	1186	51.49	2237	δ_{HCC Naphtq.} (67)
1167		1171	127.01	3980	υ_{CC Naphtq. Sym}_. (11); ρ_{HCC Naphtq}_. (14)
1140	1142	1138	52.46	252	υ_{CC Benz. Asym.} (14); ρ_{HCC Benz}_. (64)
1047		1082	90.73	73	υ_{CO Subst}_. (51); ρ_{HCCH Naphtq.} (10)
1028	1021	1050	97.77	6726	υ_{CC Naphtq. Sym.} (51)
970		979	5.17	323	t_{HCCH Benz}_. (68)
933	934	940	30.88	1653	υ_{CC Benz. Sym}_. (12); δ_CNC + δ_{CCN Naphtq.} (20)
	873	873	66.58	1271	υ_{CC Benz. Sym.} (13); δ_{CCC Naphtq.} (17); δ_{HCCC Benz.} (14)
848	855	842	118.47	1469	υ_{CC Benz. Sym.} (14); υ_{Cl-C Sym.} (15); δ_{CCC Benz.} + δ_{CC=O Naphtq.} (13); δ_{CCC Naphtq.} (10)
829		829	14.15	171	τ_{HCC Naphtq.} (47); ω_CCC=O (27); ω_{CCCC Naphtq.} (10)
818	818	822	1.15	264	ω_CC=O+ ω_{CCC Naphtq.} + τ_{HCC Naphtq}_. (63)
789	788	782	4.43	134	τ_CC=O+ ω_{CCC Naphtq.} + ω_{CCC Benz.} (18)
758	759	752	81.09	378	τ_{HCC Naphtq.} (28); ω_O=CC (33)
717	720	711	28.21	153	τ_{HCC Naphtq.} (10); τ_{CCN Naphtq}_. + ω_{CCC Naphtq.} (22); ω_{CCC Naphtq.} (11)
683		683	4.03	1332	δ_{CC=O Naphtq.}+ δ_{CCC Benz}_. + δ_{CCC Naphtq.} (28)
652	653	657	14.00	1219	δ_{CCC Benz}_. + δ_{CCC Naphtq}_. (49); δ_{CC=O Naphtq.} (13)
	641	644	43.67	14535	δ_{CCC Naphtq.}+ ω_{CCC Benz.} (15); ω_{HNCC Benz.} (31)
609		617	85.27	13870	ω_{HNC Benz}_. (49)

Experimental wavenumber / cm^-1		Calculated wavenumber / cm^-1	IR intensity / cm^-1	Raman intensity / cm^-1	PED / %
Infrared	Raman	Calculated wavenumber / cm^-1	IR intensity / cm^-1	Raman intensity / cm^-1	PED / %
3222	3228	3542	246.97	1363	υ_{NH Naphtq.} (100)
3085	3087	3233	13.00	1433	υ_{CH Naphtq. Sym.} (93)
3064	3067	3221	5.20	958	υ_{CH Benz. Sym.} (97)
	3054	3218	6.59	747	υ_{CH Naphtq. Asym.} (93)
3041	3043	3208	8.77	419	υ_{CH Benz. Asym.} (99)
2999	3002	3172	23.26	510	υ_{CH Subst. Asym.} (90)
2970	2969	3160	34.25	613	υ_{CH Subst. Asym.} (98)
2939	2936	3121	41.80	296	υ_{CH Subst. Asym.} (97)
2922		3112	40.11	282	υ_{CH Subst. Asym.} (99)
2848	2850	3045	49.55	1205	υ_{CH Subst. Sym.} (95)
2835	2836	3044	77.03	168	υ_{CH Subst. Asym.} (91)
1670	1671	1781	325.97	8125	υ_{C=O Naphtq.} (84)
1635	1636	1754	286.63	13334	υ_{C=O Naphtq.} (82)
	1609	1683	132.12	15910	υ_{CC Benz.} (56)
1593		1672	185.83	2134	υ_{CC Benz.} (11); υ_{CC Naphtq.} (43)
1564	1563	1644	955.73	11152	υ_{CC Naphtq.}+ υ_{CN Naphtq.} (36)
1520	1525	1573	877.30	1790	υ_{CN Benz.} (11); δ_{HNC Benz.}(38)
1500	1501	1561	268.95	1212	υ_{C-O Benz.} (10); δ_{HNC Benz.} (25); δ_{HCC Benz.} (27)
1467		1508	14.42	270	υ_{CC Naphtq.} (15); δ_{HCC Naphtq.} (30); ω_{HCH Subt.} (16)
	1455	1507	78.72	531	δ_{HCC Naphtq.} (12); ω_{HCH Subt.} (38)
1446		1503	51.10	1159	δ_{HCH Subt.} (60); τ_{H3CO Subt.} (14)
1421	1422	1493	16.24	402	δ_{HCH Subt.} (16); τ_{H3CO Subt.} (76)
1331		1370	286.70	3345	υ_{CC Naphtq. Asym.} (50)
1294	1293	1336	205.46	1446	υ_{CC Naphtq. Asym.}+ υ_{CC Benz. Asym.} (43)
1284		1317	413.50	1545	υ_{CC Naphtq. Asym.} + υ_{CC Benz. Asym.} (62)
1236	1235	1274	541.47	664	υ_{OC Benz.} (18); υ_{CC Benz.} (10); δ_{HCC Benz.} (13)
1221	1220	1262	81.30	1673	υ_OCBenz (22); δ_{HCC Naphtq.} (13)
1188		1222	27.56	292	δ_{HCO Subt.} (10); ω_{HCH Subt.} (50)
1157		1212	56.98	325	δ_{HCC Benz.} (10); ω_{HCH Subt.} (51)
1130	1133	1185	58.45	1863	δ_{HCC Naphtq.} (68)
1043	1041	1077	64.94	358	υ_{CO Subst.} (60); ρ_{HCCH Benz.} (19)
1026		1053	142.41	2085	υ_{CO Subst.} (64)
	1019	1049	71.11	4928	υ_{CC Naphtq. Sym.} (30); υ_{CO Subst.} (11); δ_{CC=O Naphtq.} (14)
973	975	1003	55.02	726	υ_{CC Benz.} (24)
881		891	40.77	183	δ_{CCC Naphtq.} + δ_{CCO Naphtq.} + δ_{CCN Naphtq.} (10); ω_{HCC Benz.} (65)
854		854	95.73	519	υ_{Cl-C Sym.} + υ_{CC Naphtq.} (46); δ_{CCC Naphtq.} + δ_{CCC Benz.} (15)
831		829	14.28	202	ω_{HCCC Naphtq.} (49); τ_{CCCC Naphtq.} (36)
802		802	3.52	1082	υ_{O-C Benz.} (17); τ_{CCC Benz.} (22)
769		773	29.44	2948	υ_{CC Benz.} (12); ω_{CCC Benz.} + ω_{CCC Naphtq.} (13)
748	749	749	53.18	178	τ_{HCC Naphtq.} (23); ω_{CC=O Naphtq.}(25)
719	719	711	25.43	166	ω_{CCC Naphtq.} (16); ω_{CC=O Naphtq.} (38)
685	685	688	12.12	1067	δ_{CCC Naphtq.} + ω_{CC=O Naphtq.} + τ_{CCC Benz.} (14)
654	651	660	25.71	911	δ_{CCC Naphtq.} (34); ω_{CCC Benz.} (12)
634	634	626	22.86	1823	ω_{CCC Benz.} (24)

Orbital	Energy / eV	Mulliken population	Energy / eV	Mulliken population
Orbital	1a		1b
L+4	1.16	p^{^}C=C_Benz. + p^{^}C=C_Naphtq. (6% of NH; 58% of Benz.; 36% of Naphtq.)	1.19	p^{^}C=C_Benz. + p^{^}C=C_Naphtq. (6% of NH; 57% of Benz.; 33% of Naphtq.)
L+3	0.77	p^{^*}C=C_Benz. (99% of Benz.)	0.78	p^{^*}C=C_Benz. (97% of Benz.)
L+2	0.41	p^{^}C=C_Naphtq. + p^{^}C=C_Benz. (32% of Benz.; 66% of Naphtq.)	0.45	p^{^}C=C_Naphtq. + p^{^}C=C_Benz. (29% of Benz.; 68% of Naphtq.)
L+1	-0.15	p^{^*}C=C _Naphtq. (97% of Naphtq.)	-0.13	p^{^*}C=C _Naphtq. (97% of Naphtq.)
LUMO^*	-2.10	πC=C _Naphtq. + nO (94% of Naphtq.)	-2.08	πC=C _Naphtq. + nO (94% of Naphtq.)
HOMO^*	-7.58	πC=C_Benz. + πC=C _Naphtq. + nO + nCl + nN (24% of NH; 34% of Benz.; 43% of Naphtq.)	-7.47	πC=C_Benz. + πC=C _Naphtq. + nO + nCl + nN (22% of NH; 39% of Benz.; 37% of Naphtq.)
H-1	-8.69	pC=C_Benz. + nCl (87% of Benz.; 13% of Naphtq.)	-8.59	pC=C_Benz. + nCl + pC=C _Naphtq. (64% of Benz.; 31% of Naphtq.)
H-2	-8.90	pC=C_Benz. + pC=C _Naphtq. + nCl (59% of Benz.; 39% of Naphtq.)	-8.76	pC=C_Benz. + pC=C _Naphtq. (79% of Benz.; 18% of Naphtq.)
H-3	-9.08	pC=C _Naphtq. (99% of Naphtq.)	-9.07	pC=C _Naphtq. (100% of Naphtq.)
H-4	-9.30	pC=C _Naphtq. + nO (95% of Naphtq.)	-9.28	pC=C _Naphtq. + nO (97% of Naphtq.)
H-5	-9.38	nO + sC-C_Naphtq. (5% of Benz.; 94% of Naphtq.)	-9.34	nO + sC-C_Naphtq. (97% of Naphtq.)
H-6	-10.00	nO + sC-C_Naphtq. (98% of Naphtq.)	-9.99	nO + sC-C_Naphtq. (98% of Naphtq.)
H-7	-10.63	nCl + sC-C_Naphtq. (5% of Benz.; 92% of Naphtq.)	-10.58	nCl + sC-C_Naphtq. (8% of Benz.; 90% of Naphtq.)
H-8	-10.99	nCl + pC=C_Benz. (13% of NH; 41% of Benz.; 46% of Naphtq.)	-10.84	nCl + pC=C_Benz. (14% of NH; 37% of Benz.; 44% of Naphtq.)
H-9	-11.53	nCl + sC-C_Benz. (77% of Benz.; 21% of Naphtq.)	-11.31	sC-C_Naphtq. + nCl + sC-H (74% of Benz.; 11% of Naphtq.; 12% of CH₃)
H-10	-11.76	nCl + pC=C_Naphtq+ pC=O + sC-C_Benz. (8% of NH; 32% of Benz.; 59% of Naphtq.)	-11.59	sC-C_Benz. + sC-H (62% of Benz.; 9% of Naphtq.; 26% of CH₃)
		1c		1d
L+4	1.33	p^{^}C=C_Benz. + p^{^}C=C_Naphtq. (5% of NH; 66% of Benz.; 25% of Naphtq.)	1.24	p^{^}C=C_Benz. + p^{^}C=C_Naphtq. (6% of NH; 60% of Benz.; 28% of Naphtq.)
L+3	0.69	p^{^*}C=C_Benz. (98% of Benz.)	0.95	p^{^*}C=C_Benz. (90% of Benz.; 6% of Naphtq.)
L+2	0.55	p^{^}C=C_Naphtq. + p^{^}C=C_Benz. (20% of Benz.; 76% of Naphtq.)	0.44	p^{^}C=C_Naphtq. + p^{^}C=C_Benz. (28% of Benz.; 69% of Naphtq.)
L+1	-0.11	p^{^*}C=C_Naphtq. (98% of Naphtq.)	-0.14	p^{^*}C=C_Naphtq. (97% of Naphtq.)
LUMO^*	-2.06	πC=C_Naphtq. + nO + nN (94% of Naphtq.)	-2.10	πC=C _Naphtq. + nO (94% of Naphtq.)
HOMO^*	-7.29	πC=C_Benz. + πC=C_Naphtq. + nO + nCl + nN (16% of NH; 45% of Benz.; 12% of OCH₃; 27% of Naphtq.)	-7.33	πC=C_Benz. + πC=C _Naphtq. + nO + nCl + nN (15% of NH; 48% of Benz.; 25% of Naphtq.; 5% of OCH₃; 7% of OCH₃)
H-1	-8.31	pC=C_Benz. + nO + nCl + nN (10% of NH; 30% of Benz.; 11% of OCH₃; 49% of Naphtq.)	-8.14	pC=C_Benz. + nO + nCl + pC=C _Naphtq. (8% of NH; 52% of Benz.; 22% of Naphtq.; 18% of OCH₃)
H-2	-8.85	pC=C_Benz. (95% of Benz.)	-8.61	pC=C_Benz. + nO + nCl (53% of Benz.; 35% of Naphtq.; 9% of OCH₃)
H-3	-9.06	pC=C_Naphtq. (100% of Naphtq.)	-9.07	pC=C _Naphtq. (100% of Naphtq.)
H-4	-9.26	pC=C_Naphtq. + nO (97% of Naphtq.)	-9.28	pC=C _Naphtq. (95% of Naphtq.)

Band	Dominant configuration^a a CI weights to the orbital list, shown in Table 6;	Energy / eV	f^b b oscillator strength.	Dominant configuration^a a CI weights to the orbital list, shown in Table 6;	Energy / eV	f^b b oscillator strength.
Band	1a			1b
1	73®74 (0.90)	2.95	0.1088	77®78 (0.88)	2.92	0.1174
2	70®74 (0.89) 69®74 (0.16); 71®74 (0.38); 72®74 (0.31)	4.27 4.33	0.0918 0.1565	73®78 (0.15); 75®78 (0.12); 76®78 (0.52) 74®78 (0.90)	4.23 4.28	0.1136 0.1132
3	69®74 (0.18); 71®74 (0.15); 72®74 (0.53) 68®74 (0.18); 69®74 (0.37); 71®74 (0.24) 73®75 (0.64); 73®76 (0.17)	4.74 4.96 5.14	0.0688 0.1216 0.6736	73®78 (0.20); 75®78 (0.39); 76®78 (0.27) 72®78 (0.11); 73®78 (0.44); 75®78 (0.29) 77®79 (0.63); 77®80 (0.17)	4.72 4.89 5.11	0.0618 0.1299 0.7351
4	69®75 (0.40); 70®76 (0.10); 71®75 (0.13) 70®75 (0.15); 72®77 (0.15); 73®78 (0.30); 73®79 (0.12) 65®74 (0.14); 72®76 (0.15); 73®77 (0.22)	5.98 6.30 6.44	0.0751 0.1614 0.1247	70®78 (0.86) 73®79 (0.44); 74®80 (0.10) 74®79 (0.26); 77®82 (0.20)	5.79 5.97 6.25	0.0425 0.0822 0.1940
5	63®74 (0.17); 70®76 (0.17) 71®75 (0.16); 71®77 (0.22); 72®77 (0.13)	7.00 7.18	0.3575 0.2862	66®78 (0.22); 76®80 (0.12) 66®78 (0.18); 73®79 (0.13); 74®80 (0.24)	6.97 6.97	0.3459 0.3737
	1c			1d
1	80®82 (0.16); 81®82 (0.81)	2.89	0.1194	88®90 (0.14); 89®90 (0.77)	2.90	0.1140
2	75®82 (0.46); 76®82 (0.14); 80®82 (0.22) 75®82 (0.32); 80®82 (0.41) 78®82 (0.89)	3.86 4.07 4.28	0.0222 0.0623 0.1012	82®90 (0.20); 88®90 (0.47); 89®90 (0.14) 86®90 (0.90) 85®90 (0.10); 87®90 (0.58); 88®90 (0.24)	4.04 4.27 4.36	0.0328 0.1000 0.0705
3	77®82 (0.61); 79®82 (0.12) 77®82 (0.13); 79®82 (0.34); 81®85 (0.36) 79®82 (0.19); 81®83 (0.40); 81®85 (0.16)	4.76 4.89 5.08	0.1479 0.0695 0.4993	85®90 (0.70); 87®90 (0.11) 89®91 (0.33); 89®92 (0.28); 89®93 (0.19) 89®L+1 (0.24); 89®93 (0.37)	4.82 5.03 5.17	0.1818 0.5669 0.1955
4	77®83 (0.41); 80®83 (0.12) 73®82 (0.31); 74®82 (0.18); 78®83 (0.23) 73®82 (0.12); 78®83 (0.33); 81®86 (0.12)	5.94 6.18 6.25	0.1025 0.1264 0.1689	85®91 (0.16); 89®94 (0.21) 85®91 (0.34); 89®94 (0.12) 86®91 (0.45) 88®91 (0.11); 88®92 (0.13); 88®93 (0.16); 89®93 (0.20)	5.90 5.98 6.19 6.29	0.0859 0.0999 0.1154 0.1615
5	76®84 (0.17); 79®85 (0.29); 80®84 (0.14)	6.83	0.3770	85®91 (0.17); 86®92 (0.34)	7.05	0.3516

Peak	Wavelength / nm			Assignment
Peak	MeCN	CH₂Cl₂	DMSO	Assignment
1a
1	470	473	484	pC=C_Benz. + pC=C _Naphtq. + nO + nCl + nN ® pC=C _Naphtq. + nO
2	319	327	332	pC=C _Naphtq. ® pC=C _Naphtq. + nO	pC=C_Benz. + pC=C _Naphtq. + nCl ® pC=C _Naphtq. + nO
3	275	278	279	pC=C _Naphtq. + nO ® pC=C _Naphtq. + nO	pC=C_Benz. + pC=C _Naphtq. + nO + nCl + nN ® p^{^*}C=C _Naphtq.
4	228	225^a a Estimated spectrum devolution value. n: isolated pair.		pC=C_Benz. + pC=C _Naphtq. + nO + nCl + nN ® pC=C _Naphtq. + nO	pC=C_Benz. + pC=C _Naphtq. + nO + nCl + nN ® p^{^*}C=C_Benz.
5	167^a a Estimated spectrum devolution value. n: isolated pair.			pC=C _Naphtq. ®pC=C_Benz. + pC=C _Naphtq. + nCl	pC=C_Benz. + pC=C _Naphtq. + nCl ® p^{^*}C=C_Benz.
1b
1	478	482	494	pC=C_Benz. + pC=C _Naphtq. + nO + nCl + nN ® pC=C _Naphtq. + nO
2	328	328	332	pC=C_Benz. + nCl + pC=C _Naphtq. ® pC=C _Naphtq. + nO	pC=C _Naphtq. ® pC=C _Naphtq. + nO
3	276	280	280	pC=C_Benz. + pC=C _Naphtq. + nO + nCl + nN ® p^{^*}C=C _Naphtq.	pC=C _Naphtq. + nO ® pC=C _Naphtq. + nO
4	237	231		pC=C _Naphtq. ® p^{^*}C=C _Naphtq.	pC=C _Naphtq. + nO ® p^{^*}C=C _Naphtq.
5	139^a a Estimated spectrum devolution value. n: isolated pair.			pC=C _Naphtq. ® p^{^*}C=C_Benz.	nCl + pC=C_Naphtq+ pC=O ® pC=C _Naphtq. + nO
1c
1	487	490	504	pC=C_Benz. + pC=C_Naphtq.+nO + nCl + nN ® pC=C_Naphtq. + nO + nN
2	331	335	337	pC=C_Naphtq. ® pC=C_Naphtq. + nO + nN	pC=C_Benz. + nO + nCl + nN ® pC=C_Naphtq. + nO + nN
3	277	279	281	pC=C_Benz. + pC=C_Naphtq. + nO + nCl + nN ® p^{^*}C=C_Naphtq.	C=C_Naphtq. + nO ® pC=C_Naphtq. + nO + nN
4	233	232		pC=C_Naphtq. ® p^{^*}C=C_Naphtq.	nCl + pC-N_Naphtq. + sC-C_Benz. + sC-O_Benz. ® pC=C_Naphtq. + nO + nN
5	169^a a Estimated spectrum devolution value. n: isolated pair.			pC=C_Benz. ® p^{^*}C=C_Benz.
1d
1	493	496	496	pC=C_Benz. + pC=C _Naphtq. + nO + nCl + nN ® pC=C _Naphtq. + nO
2	332	335	335	pC=C _Naphtq. ® pC=C _Naphtq. + nO	pC=C_Benz. + nO + nCl ® pC=C _Naphtq. + nO
3	280	283	283	pC=C_Benz. + pC=C _Naphtq. + nO + nCl + nN ® p^{^*}C=C_Naphtq.	pC=C _Naphtq. ® pC=C _Naphtq. + nO
4	240	230		pC=C_Benz. + nO + nCl ® p^{^*}C=C_Naphtq.	pC=C_Benz. + pC=C _Naphtq. + nO + nCl + nN ® p^{^*}C=C_Benz.
5	197^a a Estimated spectrum devolution value. n: isolated pair.			pC=C _Naphtq. ® p^{^}C=C_Naphtq. + p^{^}C=C_Benz.

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Theoretical and Experimental Spectroscopic Study on 2-Chloro-3-(substituted-phenylamino)-1,4-naphthoquinone Derivatives