They are very similar.
The only difference would be the continuity of the action. 'when' would be used for something that happened immediately after. 'I jumped when...' or 'when... I left for home'. as would be more for something that was happening previously. It would be similar to a continuous tense. 'he was still talking as the clock...'
4. September 2015
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I don't think there's much difference. If I were starting a sentence with the phrase, then I think I'd be more likely to use "as the clock struck midnight."
4. September 2015
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