The present paper describes the use of readily synthesized, environmentally benign, reusable and non-toxic iron based nanocomposite i.e iron(II) bipyridine complex immobilized to graphitic carbon nitride (Fe(bpy)3/npg-C3N4) as photocatalyst, molecular oxygen as oxidant and house hold white LED as light emitting source for the oxidative coupling of benzylamines under mild reaction conditions. The developed heterogenized homogeneous photocatalyst showed excellent activity with the added benefits of facile recovery and efficient recycling ability without any detectable loss in activity.

1. [Fe(bpy)3]2+ grafted graphitic carbon nitride hybrid for visible light
assisted oxidative coupling of benzylamines under mild reaction
conditions
Pawan Kumar, Arvind Kumar, Chetan Joshi, Srikanth Ponnada, Abhishek K. Pathak, Asgar Ali, Bojja
Sreedhar, and Suman L. Jain
Chemical Science Division, CSIR - Indian Institute of Petroleum, Dehradun - 248005, India
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Published in: Green Chem., 2016, 18, 2514–2521

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ABSTRACT
• The present paper describes the use of readily synthesized, environmentally benign,
reusable and non-toxic iron based nanocomposite i.e iron(II) bipyridine complex
immobilized to graphitic carbon nitride (Fe(bpy)3/npg-C3N4) as photocatalyst,
molecular oxygen as oxidant and house hold white LED as light emitting source for
the oxidative coupling of benzylamines under mild reaction conditions.
• The developed heterogenized homogeneous photocatalyst showed excellent activity
with the added benefits of facile recovery and efficient recycling ability without any
detectable loss in activity.
Scheme 1: Oxidative coupling of benzylamines

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Scheme 2: Synthesis of Fe(bpy)3/npg-C3N4

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Fig. 1 FE-SEM images of a) npg-
C3N4, b) Fe(bpy)3/npg-C3N4, EDX
pattern of c) npg-C3N4 and d)
Fe(bpy)3/npg-C3N4 and SEM
elemental mapping for e) C, f) N

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Fig. 2 TEM images of npg-C3N4 and
Fe(bpy)3/npg-C3N4 a), e) 200 nm, b), f) 50 nm,
c), g) 5 nm showing crystal fringes d-spacing d),
h) SAED Pattern

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Fig. 3 FTIR Spectra of a) Fe(bpy)3(PF6)2, b) npg-C3N4 and c) Fe(bpy)3/npg-C3N4

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Fig. 4 XRD Pattern of a) npg-C3N4 and b)
Fe(bpy)3/npg-C3N4

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Fig. 5 XPS survey scan of a)
npg-C3N4 b) Fe(bpy)3@npg-
C3N4 and High resolution XPS
spectra in C1s region c) and d),
in N1s region e) and f), of npg-
C3N4 and Fe(bpy)3@npg-C3N4,
in Fe 2p region g) of
Fe(bpy)3@npg-C3N4.

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Fig. 6 N2 Adsorption desorption isotherm and pore size distribution of a)
npg-C3N4 and b) Fe(bpy)3/npg-C3N4

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Fig. 7 UV-Vis absorption spectra of a) Fe(bpy)3(PF6)2 b) npg-C3N4 and c)
Fe(bpy)3@npg-C3N4

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Fig. 8 TGA graph of a) Fe(bpy)3(PF6)2 b) npg-C3N4 c) Fe(bpy)3/ npg-C3N4

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Entry Condition T/h Yield (%)b
[Fe(bpy)3](PF6)2
]
npg-C3N4 Fe(bpy)3/n
pg-C3N4
1 Dark,
CH3CN
8 6 0 3
2 Light
DCM
8 32 3 24
3 Light
CH3CN
8 98 7 94
4 Light
MeOH
8 74 9 70
5 Light
EtOH
8 72 8 67
6 Light
THF
8 65 7 57
7 Light
DMF
8 67 8 62
Table 1: Oxidative coupling of benzylamine under different reaction
conditionsa

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Fig. 9: Results of recycling experiments

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Scheme 3: Plausible mechanism of oxidative coupling of
benzylamine using Fe(bpy)3/npg-C3N4 photocatalyst

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Thanks